U.S. patent application number 12/411206 was filed with the patent office on 2009-10-01 for polymer, polymer preparation method, resist composition and patterning process.
Invention is credited to Hirofumi Io, Takeshi Kinsho, Tomohiro Kobayashi, Yuichi Okawa, Tadahiro Sunaga, Takeru WATANABE.
Application Number | 20090246686 12/411206 |
Document ID | / |
Family ID | 41117788 |
Filed Date | 2009-10-01 |
United States Patent
Application |
20090246686 |
Kind Code |
A1 |
WATANABE; Takeru ; et
al. |
October 1, 2009 |
POLYMER, POLYMER PREPARATION METHOD, RESIST COMPOSITION AND
PATTERNING PROCESS
Abstract
A polymer having a rate of dissolution in an alkaline developer
that increases under the action of acid is provided. The polymer is
prepared by reacting a hydrogenated ROMP polymer with an
O-alkylating agent in the presence of a base.
Inventors: |
WATANABE; Takeru;
(Joetsu-shi, JP) ; Kinsho; Takeshi; (Joetsu-shi,
JP) ; Kobayashi; Tomohiro; (Joetsu-shi, JP) ;
Sunaga; Tadahiro; (Sodegaura-shi, JP) ; Okawa;
Yuichi; (Sodegaura-shi, JP) ; Io; Hirofumi;
(Sodegaura-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
41117788 |
Appl. No.: |
12/411206 |
Filed: |
March 25, 2009 |
Current U.S.
Class: |
430/270.1 ;
430/326; 525/418 |
Current CPC
Class: |
Y10S 430/115 20130101;
G03F 7/0397 20130101; Y10S 430/143 20130101; C08F 283/01 20130101;
Y10S 430/106 20130101; G03F 7/0395 20130101 |
Class at
Publication: |
430/270.1 ;
525/418; 430/326 |
International
Class: |
G03F 7/004 20060101
G03F007/004; C08F 283/01 20060101 C08F283/01; G03F 7/20 20060101
G03F007/20 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 26, 2008 |
JP |
2008-080605 |
Claims
1. A polymer having a rate of dissolution in an alkaline developer
that increases under the action of acid, represented by the general
formula [1]: ##STR00085## wherein a, b, c and d indicative of
proportions of the respective recurring units relative to the
overall number of recurring units are in the range: 0<a<1,
0.ltoreq.b<1, 0.ltoreq.c<1, 0.ltoreq.d<1, and a+b+c+d=1, j
is each independently 0 or 1, k is 0 or 1, R.sup.1 is each
independently hydrogen or methyl, R.sup.2 is hydrogen or may bond
with R.sup.3 to form a ring with the carbon atoms or the carbon and
oxygen atoms to which they are attached wherein R.sup.2 and R.sup.3
taken together denote a straight, branched or cyclic
C.sub.1-C.sub.20 alkylene group which may have an oxygen functional
group, R.sup.3 is a straight, branched or cyclic C.sub.1-C.sub.20
alkyl group which may have an oxygen functional group such as
hydroxyl, ketone, ether, ester, lactone or acetal, R.sup.4 is each
independently methylene or oxygen, and R.sup.5 is a
C.sub.2-C.sub.20 acid labile group.
2. The polymer of claim 1 wherein in formula [1], the recurring
units included at proportion "a" have a lactone structure.
3. The polymer of claim 1 wherein in formula [1], k=0.
4. The polymer of claim 1 wherein in formula [1], k=1 and R.sup.3
is a straight, branched or cyclic C.sub.1-C.sub.20 alkyl group
having a hydroxyl group.
5. The polymer of claim 1 wherein in formula [1], k=1 and R.sup.3
is an acid labile group.
6. A method for preparing a polymer of formula [1] having a rate of
dissolution in an alkaline developer that increases under the
action of acid as set forth in claim 1, comprising reacting a
hydrogenated ring-opening metathesis polymer having the general
formula [2] with a compound having the general formula [3] in the
presence of a base, ##STR00086## wherein b', c and d indicative of
proportions of the respective recurring units relative to the
overall number of recurring units are in the range: 0<b'<1,
0.ltoreq.c<1, 0.ltoreq.d<1, and b'+c+d=1, j is each
independently 0 or 1, k is 0 or 1, R.sup.1 is each independently
hydrogen or methyl, R.sup.2 is hydrogen or may bond with R.sup.3 to
form a ring with the carbon atoms or the carbon and oxygen atoms to
which they are attached wherein R.sup.2 and R.sup.3 taken together
denote a straight, branched or cyclic C.sub.1-C.sub.20 alkylene
group which may have an oxygen functional group, R.sup.3 is a
straight, branched or cyclic C.sub.1-C.sub.20 alkyl group which may
have an oxygen functional group such as hydroxyl, ketone, ether,
ester, lactone or acetal, R.sup.4 is each independently methylene
or oxygen, and R.sup.5 is a C.sub.2-C.sub.20 acid labile group, and
X is a leaving group such as halogen.
7. A chemically amplified positive resist composition comprising
the polymer of claim 1 as a base resin.
8. A chemically amplified positive resist composition comprising
(A) the polymer of claim 1 as a base resin, (B) an acid generator,
(C) an organic solvent, and optionally (D) a quencher and/or (E) a
surfactant.
9. A process for forming a pattern, comprising the steps of (1)
applying the resist composition of claim 7 or 8 onto a substrate,
(2) heat treating and exposing to high-energy radiation having a
wavelength up to 300 nm or electron beam through a photomask, (3)
heat treating and developing with a developer.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This non-provisional application claims priority under 35
U.S.C. .sctn.119(a) on Patent Application No. 2008-080605 filed in
Japan on Mar. 26, 2008, the entire contents of which are hereby
incorporated by reference.
TECHNICAL FIELD
[0002] This invention relates to a polymer having a rate of
dissolution in an alkaline developer that increases under the
action of acid, a method for preparing the polymer, a resist
composition comprising the polymer as a base resin, suited for
exposure to high-energy radiation of wavelength 300 nm or less
(inclusive of excimer lasers), and a patterning process using the
resist composition.
BACKGROUND ART
[0003] While there is a continuing demand for a finer pattern rule
in the drive for higher integration and operating speeds in LSI
devices, active efforts have been devoted to develop the
microfabrication technology utilizing deep- and vacuum-ultraviolet
lithography. In particular, the ArF excimer laser (193 nm) is
widely acknowledged as a light source of next generation to the KrF
excimer laser and used in photolithography processing advanced
semiconductor devices of 90 nm node and forward. While
poly-p-hydroxystyrene derivatives played a main role as the base
resin in resist compositions of the KrF excimer laser generation,
they are difficultly applicable to the photolithography using the
ArF excimer laser as the light source because they are opaque to
wavelength 193 nm. For the ArF excimer laser photolithography, it
is the key factor to search for base resins having
transparency.
[0004] Poly(meth)acrylic acid and derivatives thereof were
considered attractive as the resins which are fully transparent at
193 nm and have relatively satisfactory development properties, but
left a problem of dry etching resistance. For improving dry etching
resistance, poly(meth)acrylate derivatives having alicyclic
structures such as adamantane and norbornane structures
incorporated in the pendant ester moiety were developed as
described in JP-A 4-39665 and JP-A 5-257281. They became the main
stream of development work.
[0005] These derivatives, however, are still insufficient in
etching resistance. It is expected from the future pattern
miniaturization trend that etching resistance will become a factor
of more significance because formation of a thinner film of resist
is essential to acquire a resolution.
[0006] Also proposed in the art are resins having an alicyclic
structure as the backbone, for example, polynorbornene derivatives
and alternating copolymers of polynorbornene derivatives and maleic
anhydride. Although some have sufficient etching resistance, there
remains unsolved the problem of poor resolution due to inferior
development properties, i.e., swelling and low dissolution contrast
during development.
[0007] Under these circumstances, a hydrogenated product of
ring-opening metathesis polymerization (ROMP) polymer was proposed
as meeting high levels of etching resistance and resolution (see
JP-A 2002-202609). The hydrogenated ROMP polymer has superior
etching resistance to the (meth)acrylate polymers due to an
alicyclic skeleton in its backbone and also exhibits good
development properties and hence good resolution probably due to a
high mobility as compared with other alicyclic polymers. This
polymer is thus quite advantageous as the base resin in ArF resist
compositions.
[0008] Nevertheless, preparation of hydrogenated ROMP polymers
requires a high precision level of polymerization and catalyst
technology, from which several problems are raised. For example,
high purity monomers which are indispensable to polymerization are
difficult to prepare, and some monomers having certain functional
groups are not susceptible to polymerization. Thus, the monomers
which can be used in industrial polymerization are limited to
certain structures. In addition, since customers currently have a
wide diversity of demands, a wide variety of base resins are
necessary to meet such demands. In the case of hydrogenated ROMP
polymers, costly labors are needed in the manufacture of a wide
variety of polymers because the overall preparation process is
relatively long and includes steps each requiring a precise
operation.
[0009] Citation List
[0010] Patent Document 1: JP-A 4-39665
[0011] Patent Document 2: JP-A 5-257281
[0012] Patent Document 3: JP-A 2002-202609 [0013] (U.S. Pat. No.
6,605,408, TW 548516)
SUMMARY OF INVENTION
[0014] An object of the invention is to provide a novel polymer, a
method for preparing the polymer, a resist composition comprising
the polymer which is suited for exposure to high-energy radiation,
and a patterning process using the resist composition.
[0015] We have discovered that by reacting a hydrogenated ROMP
polymer of specific structure which is amenable to industrial
manufacture with a specific alkylating agent, a novel polymer can
be efficiently prepared which meets all the above-discussed
properties of polymers necessary for use as the base resin in
resist compositions, specifically optical transmittance to UV and
deep-UV (inclusive of excimer lasers), dissolution in alkaline
developer, and etching resistance, and which permits some
properties to be readily tailored as desired. The polymer is
advantageously used as the base resin in resist compositions
adapted for exposure to high-energy radiation. This discovery is
surprising because polymers of analogous structure are very
difficult to manufacture in an industrial scale by the conventional
technique.
[0016] Accordingly, the invention provides a hydrogenated ROMP
polymer having a rate of dissolution in an alkaline developer that
increases under the action of acid, a method for preparing the
polymer, a resist composition comprising the polymer which is
suited for exposure to high-energy radiation, and a patterning
process using the resist composition, as defined below.
[0017] In a first aspect, the invention provides a polymer having a
rate of dissolution in an alkaline developer that increases under
the action of acid, represented by the general formula [1].
##STR00001##
Herein a, b, c and d indicative of proportions of the respective
recurring units relative to the overall number of recurring units
are in the range: 0<a<1, 0.ltoreq.b<1, 0.ltoreq.c<1,
0.ltoreq.d<1, and a+b+c+d=1, j is each independently 0 or 1, k
is 0 or 1, R.sup.1 is each independently hydrogen or methyl,
R.sup.2 is hydrogen or may bond with R.sup.3 to form a ring with
the carbon atoms or the carbon and oxygen atoms to which they are
attached wherein R.sup.2 and R.sup.3 taken together denote a
straight, branched or cyclic C.sub.1-C.sub.20 alkylene group which
may have an oxygen functional group, R.sup.3 is a straight,
branched or cyclic C.sub.1-C.sub.20 alkyl group which may have an
oxygen functional group such as hydroxyl, ketone, ether, ester,
lactone or acetal, R.sup.4 is each independently methylene or
oxygen, and R.sup.5 is a C.sub.2-C.sub.20 acid labile group.
[0018] In formula [1], the recurring units included at proportion
"a" have a lactone structure in one preferred embodiment; k=0 in
another preferred embodiment; k=1 and R.sup.3 is a straight,
branched or cyclic C.sub.1-C.sub.20 alkyl group having a hydroxyl
group in a further preferred embodiment; k=1 and R.sup.3 is an acid
labile group in a still further preferred embodiment.
[0019] In a second aspect, the invention provides a method for
preparing a polymer of formula [1] having a rate of dissolution in
an alkaline developer that increases under the action of acid as
set forth in claim 1, comprising reacting a hydrogenated
ring-opening metathesis polymer having the general formula [2] with
a compound having the general formula [3] in the presence of a
base.
##STR00002##
Herein b', c and d indicative of proportions of the respective
recurring units relative to the overall number of recurring units
are in the range: 0<b'<1, 0.ltoreq.c<1, 0.ltoreq.d<1,
and b'+c+d=1, j is each independently 0 or 1, k is 0 or 1, R.sup.1
is each independently hydrogen or methyl, R.sup.2 is hydrogen or
may bond with R.sup.3 to form a ring with the carbon atoms or the
carbon and oxygen atoms to which they are attached wherein R.sup.2
and R.sup.3 taken together denote a straight, branched or cyclic
C.sub.1-C.sub.20 alkylene group which may have an oxygen functional
group, R.sup.3 is a straight, branched or cyclic C.sub.1-C.sub.20
alkyl group which may have an oxygen functional group such as
hydroxyl, ketone, ether, ester, lactone or acetal, R.sup.4 is each
independently methylene or oxygen, and R.sup.5 is a
C.sub.2-C.sub.20 acid labile group, and X is a leaving group such
as halogen.
[0020] In a third aspect, the invention provides a chemically
amplified positive resist composition comprising the polymer
defined above as a base resin, and more specifically, a chemically
amplified positive resist composition comprising (A) the polymer
defined above as a base resin, (B) an acid generator, (C) an
organic solvent, and optionally (D) a quencher and/or (E) a
surfactant.
[0021] In a fourth aspect, the invention provides a process for
forming a pattern, comprising the steps of (1) applying the resist
composition onto a substrate to form a coating, (2) heat treating
and exposing the coating to high-energy radiation having a
wavelength up to 300 nm or electron beam through a photomask, (3)
heat treating and developing the exposed coating with a
developer.
ADVANTAGEOUS EFFECTS OF INVENTION
[0022] The novel hydrogenated ROMP polymer of the invention can be
efficiently prepared by reacting a hydrogenated ROMP polymer of
specific structure which is amenable to industrial manufacture with
a specific alkylating agent. The polymer meets all the properties
necessary for the base resin in resist compositions, specifically
optical transmittance to UV and DUV (inclusive of excimer lasers),
dissolution in alkaline developer, and etching resistance, and
permits some properties to be readily tailored as desired. A method
for preparing the polymer, a resist composition comprising the
polymer which is suited for exposure to high-energy radiation, and
a patterning process using the resist composition are provided as
well.
BRIEF DESCRIPTION OF DRAWING
[0023] The only figure, FIG. 1 is a diagram showing the .sup.1H-NMR
spectrum (600 MHz, deuterated THF) of the polymer obtained in
Example 1.
DESCRIPTION OF EMBODIMENTS
[0024] As used herein, the singular forms "a," "an" and "the"
include plural referents unless the context clearly dictates
otherwise. The notation (Cn-Cm) means a group containing from n to
m carbon atoms per group. ROMP denotes ring-opening metathesis
polymerization.
[0025] While a certain compound is herein represented by a chemical
formula, many compounds have a chemical structure for which there
can exist enantiomers or diastereomers. Each chemical formula
collectively represents all such stereoisomers whether it is either
a planar or stereostructural formula. Such stereoisomers may be
used alone or in admixture.
Polymer
[0026] The invention provides a hydrogenated ROMP polymer
comprising structural units [A] having the general formula [4] and
optionally, one or more of structural units [B] having the general
formula [5], structural units [C] having the general formula [6],
and structural units [D] having the general formula [7].
[0027] The structural units [A] have the general formula [4].
##STR00003##
[0028] In formula [4], j and k each are 0 or 1. R.sup.1 is hydrogen
or methyl. R.sup.2 is hydrogen or may bond with R.sup.3 to form a
ring with the carbon atoms or the carbon and oxygen atoms to which
they are attached wherein R.sup.2 and R.sup.3 taken together denote
a straight, branched or cyclic C.sub.1-C.sub.20 alkylene group
which may have an oxygen functional group. R.sup.3 is a straight,
branched or cyclic C.sub.1-C.sub.20 alkyl group which may have an
oxygen functional group such as hydroxyl, ketone, ether, ester,
lactone or acetal. R.sup.4 is methylene or oxygen. Suitable
examples of structural units [A] having formula [4] will be
illustrated later.
[0029] The structural units [B] have the general formula [5].
##STR00004##
[0030] In formula [5], j is 0 or 1. R.sup.1 is hydrogen or methyl.
R.sup.4 is methylene or oxygen. It is believed that structural
units [B] largely contribute to developer affinity, substrate
adhesion, and control of acid diffusion length in the inventive
resist composition. Specific examples of structural units [B]
having formula [5] are illustrated below.
##STR00005##
[0031] The structural units [C] have the general formula [6].
##STR00006##
[0032] In formula [6], j is 0 or 1. R.sup.4 is methylene or oxygen.
It is believed that structural units [C] largely contribute to
substrate adhesion and control of acid diffusion length in the
inventive resist composition. Specific examples of structural units
[C] having formula [6] are illustrated below.
##STR00007##
[0033] The structural units [D] have the general formula [7].
##STR00008##
[0034] In formula [7], j is 0 or 1. R.sup.1 is hydrogen or methyl.
R.sup.4 is methylene or oxygen. R.sup.5 is a C.sub.2-C.sub.20 acid
labile group. Structural units [D] contain an acid labile group,
that is, a group which is decomposable with the acid generated by
the acid generator upon exposure, to generate a carboxylic acid,
and contribute to resist pattern formation via development with
aqueous alkaline solution. Specific examples of structural units
[D] having formula [7] are illustrated below.
##STR00009##
[0035] In the foregoing formulae, R.sup.5 is a C.sub.2-C.sub.20
acid labile group which is exemplified by the following structural
formulae, but not limited thereto. As used herein and throughout
the specification, the broken line denotes a bonding site, Me
denotes methyl, and Et denotes ethyl.
##STR00010## ##STR00011## ##STR00012##
[0036] By virtue of structural units [A] of formula [4] introduced
therein, the polymer meets all the properties necessary as the base
resin in resist compositions and allows some properties to be
tailored as desired. Preferred examples of structural units [A]
include structural units [A-1] to [A-4], [0037] [A-1]: structural
units [A] of formula [4] having a lactone structure, [0038] [A-2]:
structural units [A] of formula [4] wherein k=0, [0039] [A-3]:
structural units [A] of formula [4] wherein k=1 and R.sup.3 is a
hydroxyl-containing straight, branched or cyclic C.sub.1-C.sub.20
alkyl group, and [0040] [A-4]: structural units [A] of formula [4]
wherein k=1 and R.sup.3 is an acid labile group.
[0041] As used herein, the "acid labile group" is a technical term
generally used in the resist-related art and refers to a group
which is deprotected under the action of acid. That is, the acid
labile group refers to a protective group for a functional group
such as carboxyl or hydroxyl, which may be decomposed or
deprotected under the action of acid through elimination reaction,
hydrolysis reaction, or substitution reaction.
[0042] When R.sup.3 denotes an acid labile group, it is a group
functioning as an acid labile group selected from the groups
defined as R.sup.3.
[0043] The introduction of structural units [A-1] into a polymer
may lead to advantages, for example, reduced risk of fine line
pattern collapsing and improved maximum resolution. Examples of
structural units [A-1] are given below, but not limited
thereto.
##STR00013## ##STR00014## ##STR00015##
[0044] The introduction of structural units [A-2] into a polymer
may lead to advantages, for example, clearer definition of spaces
in a resist pattern and improved resolution. In some cases, the
polymer may be improved in solvent solubility. Examples of
structural units [A-2] are given below, but not limited
thereto.
##STR00016## ##STR00017##
[0045] The introduction of structural units [A-3] into a polymer
may lead to advantages, for example, improved exposure latitude.
Examples of structural units [A-3] are given below, but not limited
thereto.
##STR00018## ##STR00019##
[0046] The introduction of structural units [A-4] into a polymer
may lead to advantages, for example, improved line edge roughness
(LER). When structural units [A-4] are included together with units
[D], acid labile groups of different reactivity can be assigned to
units [A-4] and [D], respectively. This advantageously increases
the freedom of polymer design in terms of decomposition upon
exposure, control of developing properties, control of thermal
properties, and solvent solubility. Examples of structural units
[A-4] are given below, but not limited thereto. In the formulae,
R.sup.6 denotes an acid labile group.
##STR00020##
[0047] The acid labile group of R.sup.6 is exemplified below, but
not limited thereto.
##STR00021## ##STR00022## ##STR00023##
[0048] In formula [1], a, b, c and d indicative of proportions of
the respective recurring units relative to the overall number of
recurring units are in the range: 0<a<1, 0.ltoreq.b<1,
0.ltoreq.c<1, 0.ltoreq.d<1, and a+b+c+d=1. That is, the
inclusion of at least structural units [A] of formula [4] is
essential. Preferably a, b, c and d are in the range:
0<a.ltoreq.0.6, 0.ltoreq.b.ltoreq.0.3, 0.ltoreq.c.ltoreq.0.7,
0.ltoreq.d.ltoreq.0.7, and more preferably 0<a.ltoreq.0.5,
0<b.ltoreq.0.2, 0.ltoreq.c.ltoreq.0.6,
0.ltoreq.d.ltoreq.0.6.
[0049] In the polymer, each of structural units [A] to [D] may be
units of one type, or either one or more or even all of structural
units [A] to [D] may consist of units of more than one type. It is
preferred that among a plurality of R.sup.4 in formulae [4] to [7]
corresponding to all these structural units [A] to [D], at least
one R.sup.4 be an oxygen atom. The inclusion of an oxygen atom in
the backbone-forming alicyclic compound is not only effective for
improving the adhesion of the polymer to silicon or other
substrates to be coated therewith, wetting tension upon development
with an aqueous alkaline solution, and the solubility of the
polymer in polar organic solvents (e.g., ketones and alcohols) used
in the step of applying the resist composition to silicon wafers,
but also effective for improving affinity to water and development
with a stripping agent or developer (e.g., aqueous alkaline
solution) following exposure. A proportion of oxygen as R.sup.4 is
0 to 99 mol %, preferably 2 to 95 mol %, more preferably 5 to 80
mol %, and most preferably 10 to 70 mol %, based on the overall
structural units.
[0050] The hydrogenated ROMP polymers typically have a weight
average molecular weight (Mw) of 500 to 200,000, preferably 2,000
to 200,000, and more preferably 3,000 to 30,000. Preferably the
polymers have a dispersity (Mw/Mn) of 1.0 to 5.0. It is noted that
the weight average molecular weight (Mw) and number average
molecular weight (Mn) of a polymer sample are determined by gel
permeation chromatography (GPC) using a solvent capable of
dissolving the sample, a column capable of separating the sample,
and polystyrene standards. The dispersity, also known as molecular
weight distribution, is defined as weight average molecular weight
(Mw) divided by number average molecular weight (Mn), i.e.,
Mw/Mn.
[0051] The polymer having a rate of dissolution in an alkaline
developer that increases under the action of acid, represented by
the general formula [1], can be efficiently prepared by reacting a
hydrogenated ROMP polymer having the general formula [2] with a
compound having the general formula [3] in the presence of a
base.
##STR00024##
[0052] In formulae [2] and [3], b', c and d indicative of
proportions of the respective recurring units relative to the
overall number of recurring units are in the range: 0<b'<1,
0.ltoreq.c<1, 0.ltoreq.d<1, and b'+c+d=1. These subscripts
are preferably in the range: 0<b'.ltoreq.0.9,
0.ltoreq.c.ltoreq.0.7, 0.ltoreq.d.ltoreq.0.7, and more preferably
0<b'.ltoreq.0.7, 0.ltoreq.c.ltoreq.0.6, 0.ltoreq.d.ltoreq.0.6.
The subscript j is each independently 0 or 1, and k is 0 or 1.
R.sup.1 is each independently hydrogen or methyl. R.sup.2 is
hydrogen or may bond with R.sup.3 to form a ring with the carbon
atoms or the carbon and oxygen atoms to which they are attached. In
the latter case, R.sup.2 and R.sup.3 taken together denote a
straight, branched or cyclic C.sub.1-C.sub.20 alkylene group which
may have an oxygen functional group. R.sup.3 is a straight,
branched or cyclic C.sub.1-C.sub.20 alkyl group which may have an
oxygen functional group such as hydroxyl, ketone, ether, ester,
lactone or acetal. R.sup.4 is each independently methylene or
oxygen. R.sup.5 is a C.sub.2-C.sub.20 acid labile group. X is a
leaving group such as halogen (e.g., chloro, bromo, iodo),
alkanesulfonyloxy or arenesulfonyloxy.
[0053] The recurring units included in a proportion b' in formula
[2] correspond to structural units [B], with their examples being
as exemplified above. The recurring units included in a proportion
c in formula [2] correspond to structural units [C], with their
examples being as exemplified above. The recurring units,included
in a proportion d in formula [2] correspond to structural units
[D], with their examples being as exemplified above.
[0054] Examples of the compound having formula [3] are given below,
but not limited thereto. In the formulae, R.sup.6 is an acid labile
group, examples of which are as exemplified above.
##STR00025## ##STR00026##
[0055] The hydrogenated ROMP polymer having formula [2] may be
prepared, for example, by providing cyclic olefin monomers
corresponding to structural units [B] of formula [5], structural
units [C] of formula [6], and structural units [D] of formula [7],
polymerizing the monomers in the presence of a ring-opening
metathesis catalyst, and hydrogenating in the presence of a
hydrogenation catalyst.
[0056] The method of preparing the hydrogenated ROMP polymer having
formula [2] is not particularly limited. For example,
polymerization and hydrogenation may be carried out by the
techniques described in JP-A 2001-354756 and JP Appln. No.
2007-272193 (U.S. Ser. No. 12/252,123). In the polymerization
reaction, any suitable catalyst may be used as long as it helps
ring-opening metathesis polymerization of the foregoing cyclic
olefin monomers. In the hydrogenation reaction, any suitable
catalyst may be used as long as it helps hydrogenation on polymers
resulting from the ring-opening metathesis polymerization. The
hydrogenated ROMP polymers having formula [2] are obtained by
producing ROMP polymers through the polymerization of cyclic olefin
monomers in the presence of a ROMP catalyst, and hydrogenating the
ROMP polymers under hydrogen pressure in a solvent in the presence
of a hydrogenation catalyst. If desired, the hydrogenated ROMP
polymers thus obtained may be subjected to acid treatment whereby
some or all acid labile groups are deprotected to generate
carboxylic acid.
[0057] The polymer having formula [1] may be prepared, as shown by
the following reaction scheme, by causing an alkylating agent
having formula [3] and a base to act on the hydrogenated ROMP
polymer having formula [2] in a solvent for effecting O-alkylating
reaction.
##STR00027##
Herein, a, b, b', c, d, j, k, R.sup.1 to R.sup.5, and X are as
defined above.
[0058] In the O-alkylating reaction, the alkylating agent [3] is
preferably used in an amount of 1.0 to 2.0 moles, more preferably
1.0 to 1.3 moles provided that the desired amount of the agent
introduced is 1 mole. The solvent used herein is not particularly
limited as long as the polymers having formulae [1] and [2] can be
dissolved therein. Preferred examples of the solvent include
hydrocarbons such as toluene; ethers such as diethylene glycol
diethyl ether, diethylene glycol dimethyl ether, and
tetrahydrofuran; ketones such as acetone, 2-butanone,
cyclohexanone, and 4-methyl-2-pentanone; alcohols such as
diethylene glycol monomethyl ether and propylene glycol monomethyl
ether; esters such as ethyl acetate, propylene glycol monomethyl
ether acetate (PGMEA), and .gamma.-butyrolactone; and aprotic polar
solvents such as N,N-dimethylformamide, N,N-dimethylacetamide,
dimethyl sulfoxide and N-methylpyrrolidone, alone or in admixture.
Suitable bases used herein include metal hydroxides such as sodium
hydroxide and potassium hydroxide; metal alkoxides such as sodium
methoxide and potassium t-butoxide; organometallic compounds such
as butyllithium and ethylmagnesium bromide; metal salts such as
potassium carbonate and sodium carbonate; and organic bases such as
pyridine, triethylamine and diisopropylethylamine, alone or in
admixture. The base is preferably used in an amount of 0.8 to 5.0
moles, and more preferably 0.9 to 2.0 moles per mole of alkylating
agent [3]. The O-alkylating reaction runs preferably at a
temperature from -20.degree. C. to around the boiling point of the
solvent used although an appropriate temperature may be selected
depending on other reaction conditions. The time of O-alkylating
reaction generally varies from about 2 hours to about 100 hours
although it is recommended to carry out a preliminary experiment to
estimate a time necessary to achieve the desired rate of
introduction. The reaction is followed by standard aqueous work-up
to remove the salt resulting from the reaction, obtaining the
desired polymer [1]. If necessary, the polymer [1] may be purified
by a standard technique such as re-precipitation or liquid
separation.
[0059] In an alternative method of preparing the polymer [1], a
monomer corresponding to structural units [A] may be introduced
from the first through polymerization reaction. However, the
foregoing method is most preferred because structural units [A] can
be introduced in any desired proportion and at an acceptable
cost.
Resist Composition
[0060] The resist composition comprising the hydrogenated ROMP
polymer of the specific structure according to the invention as a
base resin is useful as a positive working resist composition,
especially chemically amplified positive working resist
composition. In addition to the hydrogenated ROMP polymer as a base
resin, the composition contains essentially (B) a compound capable
of generating an acid in response to high-energy radiation or
electron beam (known as acid generator) and (C) an organic solvent
and optionally, (D) a compound capable of suppressing acid
diffusion within a resist film (known as quencher) and (E) a
surfactant.
[0061] Acid Generator
[0062] In the resist composition of the invention, an acid
generator is generally included. A typical acid generator is a
photoacid generator (PAG) which may be any compound capable of
generating an acid in response to high-energy radiation such as UV,
deep-UV, electron beam, X-ray, excimer laser, .gamma.-ray and
synchrotron radiation. Suitable photoacid generators include
sulfonium salts, iodonium salts, sulfonyldiazomethane,
N-sulfonyloxydicarboximide, O-arylsulfonyloxime and
O-alkylsulfonyloxime acid generators. Exemplary photoacid
generators are given below while they may be used alone or in
admixture of two or more.
[0063] Sulfonium salts are salts of sulfonium cations with
sulfonates, bis(substituted alkylsulfonyl)imides and
tris(substituted alkylsulfonyl)methides. Exemplary sulfonium
cations include triphenylsulfonium,
(4-tert-butoxyphenyl)diphenylsulfonium,
bis(4-tert-butoxyphenyl)phenylsulfonium,
tris(4-tert-butoxyphenyl)sulfonium,
(3-tert-butoxyphenyl)diphenylsulfonium,
bis(3-tert-butoxyphenyl)phenylsulfonium,
tris(3-tert-butoxyphenyl)sulfonium,
(3,4-di-tert-butoxyphenyl)diphenylsulfonium,
bis(3,4-di-tert-butoxyphenyl)phenylsulfonium,
tris(3,4-di-tert-butoxyphenyl)sulfonium,
diphenyl(4-thiophenoxyphenyl)sulfonium,
(4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium,
tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium,
(4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium,
tris(4-dimethylaminophenyl)sulfonium,
4-methylphenyldiphenylsulfonium, 4-tert-butylphenylsulfonium,
bis(4-methylphenyl)phenylsulfonium,
bis(4-tert-butylphenyl)phenylsulfonium,
tris(4-methylphenyl)sulfonium, tris(4-tert-butylphenyl)sulfonium,
tris(phenylmethyl)sulfonium, 2-naphthyldiphenylsulfonium,
dimethyl(2-naphthyl)sulfonium, 4-hydroxyphenyldimethylsulfonium,
4-methoxyphenyldimethylsulfonium, trimethylsulfonium,
2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium,
tribenzylsulfonium, diphenylmethylsulfonium,
dimethylphenylsulfonium, 2-oxopropylthiacyclopentanium,
2-oxobutylthiacyclopentanium,
2-oxo-3,3-dimethylbutylthiacyclopentanium,
2-oxo-2-phenylethylthiacyclopentanium,
4-n-butoxynaphthyl-1-thiacyclopentanium, and
2-n-butoxynaphthyl-1-thiacyclopentanium. Exemplary sulfonates
include trifluoromethanesulfonate, pentafluoroethanesulfonate,
heptafluoropropanesulfonate, nonafluorobutanesulfonate,
tridecafluorohexanesulfonate,
perfluoro(4-ethylcyclohexane)sulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate,
4-fluorobenzenesulfonate, mesitylenesulfonate,
2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,
benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,
6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,
4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,
1,1-difluoro-2-naphthylethanesulfonate,
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,
1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-en-8-
-yl)ethanesulfonate,
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate. Exemplary
bis(substituted alkylsulfonyl)imides include
bis(trifluoromethylsulfonyl)imide,
bis(pentafluoroethylsulfonyl)imide,
bis(heptafluoropropylsulfonyl)imide, and
perfluoro(1,3-propylenebissulfonyl)imide. A typical
tris(substituted alkylsulfonyl)methide is
tris(trifluoromethylsulfonyl)methide. Sulfonium salts based on
combination of the foregoing examples are included.
[0064] Iodonium salts are salts of iodonium cations with
sulfonates, bis(substituted alkylsulfonyl)imides and
tris(substituted alkylsulfonyl)methides. Exemplary iodonium cations
include diphenyliodinium, bis(4-tert-butylphenyl)iodonium,
4-tert-butoxyphenylphenyliodonium, and
4-methoxyphenylphenyliodonium. Exemplary sulfonates include
trifluoromethanesulfonate, pentafluoroethanesulfonate,
heptafluoropropanesulfonate, nonafluorobutanesulfonate,
tridecafluorohexanesulfonate,
perfluoro(4-ethylcyclohexane)sulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate,
4-fluorobenzenesulfonate, mesitylenesulfonate,
2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,
benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,
6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,
4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,
1,1-difluoro-2-naphthylethanesulfonate,
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,
1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-en-8-
-yl)ethanesulfonate,
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate. Exemplary
bis(substituted alkylsulfonyl)imides include
bis(trifluoromethylsulfonyl)imide,
bis(pentafluoroethylsulfonyl)imide,
bis(heptafluoropropylsulfonyl)imide, and
perfluoro(1,3-propylenebissulfonyl)imide. A typical
tris(substituted alkylsulfonyl)methide is
tris(trifluoromethylsulfonyl)methide. Iodonium salts based on
combination of the foregoing examples are included.
[0065] Exemplary sulfonyldiazomethane compounds include
bissulfonyldiazomethane compounds and sulfonyl-carbonyldiazomethane
compounds such as bis(ethylsulfonyl)diazomethane,
bis(1-methylpropylsulfonyl)diazomethane,
bis(2-methylpropylsulfonyl)diazomethane,
bis(1,1-dimethylethylsulfonyl)diazomethane,
bis(cyclohexylsulfonyl)diazomethane,
bis(perfluoroisopropylsulfonyl)diazomethane,
bis(phenylsulfonyl)diazomethane,
bis(4-methylphenylsulfonyl)diazomethane,
bis(2,4-dimethylphenylsulfonyl)diazomethane,
bis(4-acetyloxyphenylsulfonyl)diazomethane,
bis(4-(methanesulfonyloxy)phenylsulfonyl)diazomethane,
bis(4-(p-toluenesulfonyloxy)phenylsulfonyl)diazomethane,
bis(4-(n-hexyloxy)phenylsulfonyl)diazomethane,
bis(2-methyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,
bis(2,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,
bis(3,5-dimethyl-4-(n-hexyloxy)phenylsulfonyl)diazomethane,
bis(2-methyl-5-isopropyl-4-(n-hexyloxy)phenylsulfonyl)diazo-methane,
bis(2-naphthylsulfonyl)diazomethane,
4-methylphenylsulfonylbenzoyldiazomethane,
tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane,
2-naphthylsulfonylbenzoyldiazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane,
methylsulfonylbenzoyldiazomethane, and
tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.
[0066] N-sulfonyloxydicarboximide photoacid generators include
combinations of imide skeletons with sulfonates. Exemplary imide
skeletons are succinimide, naphthalenedicarboximide, phthalimide,
cyclohexyldicarboximide, 5-norbornene-2,3-dicarboximide, and
7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboximide. Exemplary
sulfonates include trifluoromethanesulfonate,
pentafluoroethanesulfonate, heptafluoropropanesulfonate,
nonafluorobutanesulfonate, tridecafluorohexanesulfonate,
perfluoro(4-ethylcyclohexane)sulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate,
4-fluorobenzenesulfonate, mesitylenesulfonate,
2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,
benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,
6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,
4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,
1,1-difluoro-2-naphthylethanesulfonate,
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,
1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-en-8-
-yl)ethanesulfonate,
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0067] Benzoinsulfonate photoacid generators include benzoin
tosylate, benzoin mesylate, and benzoin butanesulfonate.
[0068] Pyrogallol trisulfonate photoacid generators include
pyrogallol, phloroglucinol, catechol, resorcinol, and hydroquinone,
in which all the hydroxyl groups are substituted by
trifluoromethanesulfonate, pentafluoroethanesulfonate,
heptafluoropropanesulfonate, nonafluorobutanesulfonate,
tridecafluorohexanesulfonate,
perfluoro(4-ethylcyclohexane)sulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate,
4-fluorobenzenesulfonate, mesitylenesulfonate,
2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,
benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,
6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,
4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,
1,1-difluoro-2-naphthylethanesulfonate,
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,
1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-en-8-
-yl)ethanesulfonate,
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0069] Nitrobenzyl sulfonate photoacid generators include
2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and
2,6-dinitrobenzyl sulfonate, with exemplary sulfonates including
trifluoromethanesulfonate, pentafluoroethanesulfonate,
heptafluoropropanesulfonate, nonafluorobutanesulfonate,
tridecafluorohexanesulfonate,
perfluoro(4-ethylcyclohexane)sulfonate,
heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate,
pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate,
4-fluorobenzenesulfonate, mesitylenesulfonate,
2,4,6-triisopropylbenzenesulfonate, toluenesulfonate,
benzenesulfonate, 4-(p-toluenesulfonyloxy)benzenesulfonate,
6-(p-toluenesulfonyloxy)naphthalene-2-sulfonate,
4-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
5-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
8-(p-toluenesulfonyloxy)naphthalene-1-sulfonate,
naphthalenesulfonate, camphorsulfonate, octanesulfonate,
dodecylbenzenesulfonate, butanesulfonate, methanesulfonate,
1,1-difluoro-2-naphthylethanesulfonate,
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate,
1,1,2,2-tetrafluoro-2-(tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-en-8-
-yl)ethanesulfonate,
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate. Also useful
are analogous nitrobenzyl sulfonate compounds in which the nitro
group on the benzyl side is substituted by a trifluoromethyl
group.
[0070] Sulfone photoacid generators include [0071]
bis(phenylsulfonyl)methane, [0072]
bis(4-methylphenylsulfonyl)methane, [0073]
bis(2-naphthylsulfonyl)methane, [0074]
2,2-bis(phenylsulfonyl)propane, [0075]
2,2-bis(4-methylphenylsulfonyl)propane, [0076]
2,2-bis(2-naphthylsulfonyl)propane, [0077]
2-methyl-2-(p-toluenesulfonyl)propiophenone, [0078]
2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, and [0079]
2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.
[0080] Suitable O-arylsulfonyloxime compounds and
O-alkylsulfonyloxime compounds (oxime sulfonates) include photoacid
generators in the form of glyoxime derivatives; photoacid
generators in the form of oxime sulfonates with a long conjugated
system separated by thiophene or cyclohexadiene; oxime sulfonates
having an electron withdrawing group such as trifluoromethyl
incorporated for increased stability; oxime sulfonates using
phenylacetonitrile or substituted acetonitrile derivatives; and
bisoxime sulfonates.
[0081] Photoacid generators in the form of glyoxime derivatives
include bis-O-(p-toluenesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(p-toluenesulfonyl)-.alpha.-diphenylglyoxime,
bis-O-(p-toluenesulfonyl)-.alpha.-dicyclohexylglyoxime,
bis-O-(p-toluenesulfonyl)-2,3-pentanedionedioxime,
bis-O-(n-butanesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(n-butanesulfonyl)-.alpha.-diphenylglyoxime,
bis-O-(n-butanesulfonyl)-.alpha.-dicyclohexylglyoxime,
bis-O-(methanesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(trifluoromethanesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(2,2,2-trifluoroethanesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(10-camphorsulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(benzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(4-fluorobenzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(4-trifluoromethylbenzenesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(xylenesulfonyl)-.alpha.-dimethylglyoxime,
bis-O-(trifluoromethanesulfonyl)-nioxime,
bis-O-(2,2,2-trifluoroethanesulfonyl)-nioxime,
bis-O-(10-camphorsulfonyl)-nioxime,
bis-O-(benzenesulfonyl)-nioxime,
bis-O-(4-fluorobenzenesulfonyl)-nioxime,
bis-O-(4-(trifluoromethyl)benzenesulfonyl)-nioxime, and
bis-O-(xylenesulfonyl)-nioxime. Also included are modified forms of
the foregoing compounds having substituted on their skeleton
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxycarbonyldifluoromethanesulfonate,
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0082] Photoacid generators in the form of oxime sulfonates with a
long conjugated system separated by thiophene or cyclohexadiene
include [0083]
(5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)phenyl-acetonitrile,
[0084]
(5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)phenyl-aceto-
nitrile, [0085]
(5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)phenyl-acetonitrile,
[0086]
(5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphen-
yl)acetonitrile, [0087]
(5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)ace-
tonitrile, [0088]
(5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene)(2-methyl-phenyl)aceton-
itrile, [0089]
(5-(4-(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-yliden-
e)phenylacetonitrile, and [0090]
(5-(2,5-bis(p-toluenesulfonyloxy)benzenesulfonyl)oxyimino-5H-thiophen-2-y-
lidene)phenylacetonitrile.
[0091] Also included are modified forms of the foregoing compounds
having substituted on their skeleton [0092]
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0093]
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
[0094] 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, [0095]
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
[0096] 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, [0097]
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0098]
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0099]
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0100] 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0101]
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, [0102]
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, [0103]
1,1-difluoro-2-tosyloxyethanesulfonate, [0104]
adamantanemethoxycarbonyldifluoromethanesulfonate, [0105]
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
[0106] methoxycarbonyldifluoromethanesulfonate, [0107]
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and [0108]
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0109] Suitable oxime sulfonates having an electron withdrawing
group such as trifluoromethyl incorporated for increased stability
include 2,2,2-trifluoro-1-phenyl-ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-phenyl-ethanone O-(10-camphorsulfonyl)oxime,
2,2,2-trifluoro-1-phenylethanone O-(4-methoxybenzenesulfonyl)oxime,
2,2,2-trifluoro-1-phenyl-ethanone O-(1-naphthylsulfonyl)oxime,
2,2,2-trifluoro-1-phenylethanone O-(2-naphthylsulfonyl)oxime,
2,2,2-trifluoro-1-phenylethanone
O-(2,4,6-trimethylphenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylphenyl)ethanone
O-(10-camphor-sulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylphenyl)ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(2-methylphenyl)-ethanone
O-(10-camphorsulfonyl)oxime,
2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanone
O-(10-camphorsulfonyl)oxime,
2,2,2-trifluoro-1-(2,4-dimethylphenyl)ethanone
O-(1-naphthyl-sulfonyl)oxime,
2,2,2-trifluoro-1-(2,4-dimethylphenyl)-ethanone
O-(2-naphthylsulfonyl)oxime,
2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone
O-(10-camphorsulfonyl)oxime,
2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)ethanone
O-(1-naphthylsulfonyl)oxime,
2,2,2-trifluoro-1-(2,4,6-trimethyl-phenyl)ethanone
O-(2-naphthylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone
O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylthiophenyl)-ethanone
O-(methyl-sulfonyl)oxime,
2,2,2-trifluoro-1-(3,4-dimethoxyphenyl)-ethanone
O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone
O-(4-methylphenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone
O-(4-methoxy-phenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone
O-(4-dodecylphenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxyphenyl)ethanone O-(octylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone
O-(4-methoxy-phenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-thiomethylphenyl)-ethanone
O-(4-dodecylphenylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone
O-(octylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-thiomethylphenyl)ethanone
O-(2-naphthyl-sulfonyl)oxime,
2,2,2-trifluoro-1-(2-methylphenyl)ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylphenyl)-ethanone
O-(phenylsulfonyl)oxime, 2,2,2-trifluoro-1-(4-chlorophenyl)ethanone
O-(phenylsulfonyl)oxime, 2,2,3,3,4,4,4-heptafluoro-1-phenylbutanone
O-(10-camphor-sulfonyl)oxime,
2,2,2-trifluoro-1-(1-naphthyl)ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(2-naphthyl)-ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-benzylphenyl)ethanone O-(methylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-(phenyl-1,4-dioxa-but-1-yl)phenyl)ethanone
O-(methylsulfonyl)oxime, 2,2,2-trifluoro-1-(1-naphthyl)ethanone
O-(propylsulfonyl)oxime, 2,2,2-trifluoro-1-(2-naphthyl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-benzylphenyl)-ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylsulfonylphenyl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methylsulfonyloxyphenyl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methyl-carbonyloxyphenyl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(6H,7H-5,8-dioxonaphth-2-yl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxy-carbonylmethoxyphenyl)ethanone
O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl)phenyl)eth-
anone O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(3,5-dimethyl-4-ethoxyphenyl)ethanone
O-(propylsulfonyl)-oxime,
2,2,2-trifluoro-1-(4-benzyloxyphenyl)ethanone
O-(propylsulfonyl)oxime, 2,2,2-trifluoro-1-(2-thiophenyl)-ethanone
O-(propylsulfonate)oxime, and
2,2,2-trifluoro-1-(1-dioxathiophen-2-yl)ethanone
O-(propylsulfonate)oxime;
2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(trifluoro-methanesulfonylo-
xyimino)ethyl)phenoxy)propoxy)phenyl)ethanone
O-(trifluoromethanesulfonyl)oxime,
2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(1-propanesulfonyloxyimino)-
ethyl)-phenoxy)propoxy)phenyl)ethanone O-(propylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(1-butane-sulfonyloxyimino)-
ethyl)phenoxy)propoxy)phenyl)ethanone O-(butylsulfonyl)oxime,
2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(4-(4-methylphenylsulfonylo-
xy)phenylsulfonyl-oxyimino)ethyl)phenoxy)propoxy)phenyl)ethanone
O-(4-(4-methylphenylsulfonyloxy)phenylsulfonyl)oxime, and
2,2,2-trifluoro-1-(4-(3-(4-(2,2,2-trifluoro-1-(2,5-bis(4-methylphenylsulf-
onyloxy)benzenesulfonyloxy)phenylsulfonyloxy-imino)ethyl)phenoxy)propoxy)p-
henyl)ethanone
O-(2,5-bis(4-methylphenylsulfonyloxy)benzenesulfonyloxy)phenylsulfonyl)-o-
xime. Also included are modified forms of the foregoing compounds
having substituted on their skeleton
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane-sulfonate,
1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate,
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoro-propanesulfonate,
2-acetyloxy-1,1,3,3,3-pentafluoropropane-sulfonate,
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate,
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate,
1,1-difluoro-2-tosyloxyethanesulfonate,
adamantanemethoxy-carbonyldifluoromethanesulfonate,
1-(3-hydroxymethyl-adamantane)methoxycarbonyldifluoromethanesulfonate,
methoxycarbonyldifluoromethanesulfonate,
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxycarbonyl)difl-
uoro-methanesulfonate, and
4-oxo-1-adamantyloxycarbonyldifluoro-methanesulfonate.
[0110] Also included are oxime sulfonates having the formula
(Ox-1):
##STR00028##
wherein R.sup.401 is a substituted or unsubstituted
C.sub.1-C.sub.10 haloalkylsulfonyl or halobenzenesulfonyl group,
R.sup.402 is a C.sub.1-C.sub.11 haloalkyl group, and Ar.sup.401 is
substituted or unsubstituted aromatic or hetero-aromatic group.
Examples include [0111]
2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxy-imino)-pentyl-
]fluorene, [0112]
2-[2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxy-imino)-butyl]flu-
orene, [0113]
2-[2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyl-oxyimino)-he-
xyl]fluorene, [0114]
2-[2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxy-imino)-pentyl-
]-4-biphenyl, [0115]
2-[2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxy-imino)-butyl]-4--
biphenyl, and [0116]
2-[2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyl-oxyimino)-he-
xyl]-4-biphenyl. Also included are modified forms of the foregoing
compounds having substituted on their skeleton
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0117]
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
[0118] 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, [0119]
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane-sulfonate,
[0120] 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, [0121]
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0122]
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0123]
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0124] 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0125]
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, [0126]
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, [0127]
1,1-difluoro-2-tosyloxyethanesulfonate, [0128]
adamantanemethoxycarbonyldifluoromethanesulfonate, [0129]
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
[0130] methoxycarbonyldifluoromethanesulfonate, [0131]
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and [0132]
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0133] Suitable oxime sulfonate generators using substituted
acetonitrile derivatives include [0134]
.alpha.-(p-toluenesulfonyloxyimino)-phenylacetonitrile, [0135]
.alpha.-(p-chlorobenzenesulfonyloxyimino)-phenylacetonitrile,
[0136] .alpha.-(4-nitrobenzenesulfonyloxyimino)-phenylacetonitrile,
[0137]
.alpha.-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-phenylacetonit-
rile, [0138]
.alpha.-(benzenesulfonyloxyimino)-4-chlorophenylacetonitrile,
[0139]
.alpha.-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile,
[0140]
.alpha.-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile,
[0141]
.alpha.-(benzenesulfonyloxyimino)-4-methoxyphenylacetonitrile,
[0142]
.alpha.-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylaceto-nit-
rile, [0143]
.alpha.-(benzenesulfonyloxyimino)-2-thienylacetonitrile, [0144]
.alpha.-(4-dodecylbenzenesulfonyloxyimino)-phenylacetonitrile,
[0145]
.alpha.-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,
[0146]
.alpha.-[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl]aceto-ni-
trile, [0147] .alpha.-(tosyloxyimino)-3-thienylacetonitrile, [0148]
.alpha.-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile,
[0149] .alpha.-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile,
[0150]
.alpha.-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile,
[0151]
.alpha.-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile,
[0152] .alpha.-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile,
[0153]
.alpha.-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, and
[0154]
.alpha.-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile.
[0155] Also included are modified forms of the foregoing compounds
having substituted on their skeleton [0156]
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0157]
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
[0158] 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, [0159]
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
[0160] 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, [0161]
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0162]
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0163]
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0164] 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0165]
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, [0166]
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, [0167]
1,1-difluoro-2-tosyloxyethanesulfonate, [0168]
adamantanemethoxycarbonyldifluoromethanesulfonate, [0169]
1-(3-hydroxymethyladamantane)methoxycarbonyldifluoromethane-sulfonate,
[0170] methoxycarbonyldifluoromethanesulfonate, [0171]
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]fluran-6-yloxy-carbonyl)di-
fluoromethanesulfonate, and [0172]
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0173] Suitable bisoxime sulfonates include [0174]
bis(.alpha.-(p-toluenesulfonyloxy)imino)-p-phenylenediacetonitrile,
[0175]
bis(.alpha.-(benzenesulfonyloxy)imino)-p-phenylenediacetonitrile,
[0176]
bis(.alpha.-(methanesulfonyloxy)imino)-p-phenylenediacetonitrile,
[0177]
bis(.alpha.-(butanesulfonyloxy)imino)-p-phenylenediacetonitrile,
[0178]
bis(.alpha.-(10-camphorsulfonyloxy)imino)-p-phenylenediaceto-nitri-
le, [0179]
bis(.alpha.-(trifluoromethanesulfonyloxy)imino)-p-phenylenediac-
eto-nitrile, [0180]
bis(.alpha.-(4-methoxybenzenesulfonyloxy)imino)-p-phenylenediaceto-nitril-
e, [0181]
bis(.alpha.-(p-toluenesulfonyloxy)imino)-m-phenylenediacetonitri-
le, [0182]
bis(.alpha.-(benzenesulfonyloxy)imino)-m-phenylenediacetonitril- e,
[0183]
bis(.alpha.-(methanesulfonyloxy)imino)-m-phenylenediacetonitrile- ,
[0184]
bis(.alpha.-(butanesulfonyloxy)imino)-m-phenylenediacetonitrile,
[0185]
bis(.alpha.-(10-camphorsulfonyloxy)imino)-m-phenylenediaceto-nitri-
le, [0186]
bis(.alpha.-(trifluoromethanesulfonyloxy)imino)-m-phenylenediac-
eto-nitrile, [0187]
bis(.alpha.-(4-methoxybenzenesulfonyloxy)imino)-m-phenylenediaceto-nitril-
e, etc. Also included are modified forms of the foregoing compounds
having substituted on their skeleton
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate,
1,1,3,3,3-pentafluoro-2-(4-phenylbenzoyloxy)propanesulfonate,
1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate,
2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane-sulfonate,
[0188] 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, [0189]
2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0190]
2-(4-tert-butylbenzoyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0191]
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane-sulfonate,
[0192] 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0193]
1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, [0194]
1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, [0195]
1,1-difluoro-2-tosyloxyethanesulfonate, [0196]
adamantanemethoxycarbonyldifluoromethanesulfonate,1-(3-hydroxymethyladama-
ntane)methoxycarbonyldifluoromethane-sulfonate, [0197]
methoxycarbonyldifluoromethanesulfonate, [0198]
1-(hexahydro-2-oxo-3,5-methano-2H-cyclopenta[b]furan-6-yloxy-carbonyl)dif-
luoromethanesulfonate, and [0199]
4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.
[0200] When the photoacid generator (B) is added to the KrF excimer
laser resist composition, preference is given to sulfonium salts,
bissulfonyldiazomethanes, N-sulfonyloxyimides and
oxime-O-sulfonates. Illustrative preferred photoacid generators
include [0201] triphenylsulfonium p-toluenesulfonate, [0202]
triphenylsulfonium camphorsulfonate, [0203] triphenylsulfonium
pentafluorobenzenesulfonate, [0204] triphenylsulfonium
nonafluorobutanesulfonate, [0205] triphenylsulfonium
4-(p-toluenesulfonyloxy)benzenesulfonate, [0206] triphenylsulfonium
2,4,6-triisopropylbenzenesulfonate, [0207]
4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate, [0208]
4-tert-butoxyphenyldiphenylsulfonium camphorsulfonate, [0209]
4-tert-butoxyphenyldiphenylsulfonium
4-(p-toluenesulfonyl-oxy)benzenesulfonate, [0210]
4-tert-butylphenyldiphenylsulfonium camphorsulfonate, [0211]
tris(4-methylphenyl)sulfonium camphorsulfonate, [0212]
tris(4-tert-butylphenyl)sulfonium camphorsulfonate, [0213]
bis(tert-butylsulfonyl)diazomethane, [0214]
bis(cyclohexylsulfonyl)diazomethane, [0215]
bis(2,4-dimethylphenylsulfonyl)diazomethane, [0216]
bis(4-n-hexyloxyphenylsulfonyl)diazomethane, [0217]
bis(2-methyl-4-n-hexyloxyphenylsulfonyl)diazomethane, [0218]
bis(2,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane, [0219]
bis(3,5-dimethyl-4-n-hexyloxyphenylsulfonyl)diazomethane, [0220]
bis(2-methyl-5-isopropyl-4-n-hexyloxy)phenylsulfonyldiazo-methane,
[0221] bis(4-tert-butylphenylsulfonyl)diazomethane, [0222]
N-camphorsulfonyloxy-5-norbornene-2,3-dicarboxylic acid imide,
[0223] N-p-toluenesulfonyloxy-5-norbornene-2,3-dicarboxylic acid
imide, [0224]
(5-(10-camphorsulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)ace-
tonitrile, and [0225]
(5-(p-toluenesulfonyl)oxyimino-5H-thiophen-2-ylidene)(2-methylphenyl)acet-
onitrile.
[0226] When the photoacid generator (B) is added to the ArF laser
resist composition, preference is given to sulfonium salts and
oxime-O-sulfonates. Illustrative preferred photoacid generators
include [0227] triphenylsulfonium trifluoromethanesulfonate, [0228]
triphenylsulfonium pentafluoroethanesulfonate, [0229]
triphenylsulfonium heptafluoropropanesulfonate, [0230]
triphenylsulfonium nonafluorobutanesulfonate, [0231]
triphenylsulfonium tridecafluorohexanesulfonate, [0232]
triphenylsulfonium heptadecafluorooctanesulfonate, [0233]
triphenylsulfonium perfluoro(4-ethylcyclohexane)sulfonate, [0234]
4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate, [0235]
2-oxo-2-phenylethylthiacyclopentanium nonafluorobutane-sulfonate,
[0236] 4-tert-butylphenyldiphenylsulfonium
nonafluorobutanesulfonate, [0237]
4-tert-butylphenyldiphenylsulfonium
perfluoro(4-ethylcyclo-hexane)sulfonate, [0238]
4-tert-butylphenyldiphenylsulfonium heptafluorooctane-sulfonate,
[0239] triphenylsulfonium 1,1-difluoro-2-naphthylethanesulfonate,
[0240] triphenylsulfonium
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)-ethanesulfonate, [0241]
triphenylsulfonium
2-benzoyloxy-1,1,3,3,3-pentafluoropropane-sulfonate, [0242]
triphenylsulfonium
1,1,3,3,3-pentafluoro-2-(pivaloyloxy)-propanesulfonate, [0243]
triphenylsulfonium
2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0244] triphenylsulfonium
2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoro-propanesulfonate, [0245]
triphenylsulfonium
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0246] triphenylsulfonium
2-hydroxy-1,1,3,3,3-pentafluoropropane-sulfonate, [0247]
triphenylsulfonium
adamantanemethoxycarbonyldifluoromethane-sulfonate, [0248]
triphenylsulfonium
1-(3-hydroxymethyladamantane)methoxy-carbonyldifluoromethanesulfonate,
[0249] triphenylsulfonium methoxycarbonyldifluoromethanesulfonate,
[0250] 4-tert-butylphenyldiphenylsulfonium
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0251]
4-tert-butylphenyldiphenylsulfonium
1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propanesulfonate, [0252]
4-tert-butylphenyldiphenylsulfonium
2-(cyclohexanecarbonyl-oxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0253] 4-tert-butylphenyldiphenylsulfonium
2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate, [0254]
4-tert-butylphenyldiphenylsulfonium
2-(1-adamantanecarbonyl-oxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0255] 4-tert-butylphenyldiphenylsulfonium
2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate, [0256]
4-tert-butylphenyldiphenylsulfonium
adamantanemethoxy-carbonyldifluoromethanesulfonate, [0257]
4-tert-butylphenyldiphenylsulfonium
1-(3-hydroxymethyl-adamantane)methoxycarbonyldifluoromethanesulfonate,
[0258] 4-tert-butylphenyldiphenylsulfonium
methoxycarbonyldifluoro-methanesulfonate, [0259]
2-oxo-2-phenylethylthiacyclopentanium
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0260]
2-oxo-2-phenylethylthiacyclopentanium
2-cyclohexanecarbonyl-oxy-1,1,3,3,3-pentafluoropropanesulfonate,
[0261] triphenylsulfonium perfluoro(1,3-propylenebissulfonyl)imide,
[0262] triphenylsulfonium bis(pentafluoroethylsulfonyl)imide,
[0263]
2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxy-imino)pentyl)-
fluorene, [0264]
2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxy-imino)butyl)fluo-
rene, [0265]
2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyl-oxyimino)hex-
yl)fluorene, [0266]
2-(2,2,3,3,4,4,5,5-octafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pen-
tafluoropropanesulfonyloxyimino)pentyl)fluorene, [0267]
2-(2,2,3,3,4,4-pentafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentaf-
luoropropanesulfonyloxyimino)butyl)fluorene, [0268] and
2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutyl-sulfonyloxyimino)hex-
yl)fluorene.
[0269] When the photoacid generator (B) is added to the ArF
immersion lithography resist composition, preference is given to
sulfonium salts and oxime-O-sulfonates. Illustrative preferred
photoacid generators include [0270] triphenylsulfonium
nonafluorobutanesulfonate, [0271] triphenylsulfonium
tridecafluorohexanesulfonate, [0272] triphenylsulfonium
heptadecafluorooctanesulfonate, [0273] triphenylsulfonium
perfluoro(4-ethylcyclohexane)sulfonate, [0274]
4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate, [0275]
2-oxo-2-phenylethylthiacyclopentanium nonafluorobutane-sulfonate,
[0276] 4-tert-butylphenyldiphenylsulfonium
nonafluorobutanesulfonate, [0277]
4-tert-butylphenyldiphenylsulfonium
perfluoro(4-ethylcyclo-hexane)sulfonate, [0278]
4-tert-butylphenyldiphenylsulfonium heptafluorooctane-sulfonate,
[0279] triphenylsulfonium 1,1-difluoro-2-naphthylethanesulfonate,
[0280] triphenylsulfonium
1,1,2,2-tetrafluoro-2-(norbornan-2-yl)-ethanesulfonate, [0281]
triphenylsulfonium
2-benzoyloxy-1,1,3,3,3-pentafluoropropane-sulfonate, [0282]
triphenylsulfonium
1,1,3,3,3-pentafluoro-2-(pivaloyloxy)-propanesulfonate, [0283]
triphenylsulfonium
2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0284] triphenylsulfonium
2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoro-propanesulfonate, [0285]
triphenylsulfonium
2-(1-adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0286] triphenylsulfonium
2-hydroxy-1,1,3,3,3-pentafluoropropane-sulfonate, [0287]
triphenylsulfonium
adamantanemethoxycarbonyldifluoromethane-sulfonate, [0288]
triphenylsulfonium
1-(3-hydroxymethyladamantane)methoxy-carbonyldifluoromethanesulfonate,
[0289] triphenylsulfonium methoxycarbonyldifluoromethanesulfonate,
[0290] 4-tert-butylphenyldiphenylsulfonium
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0291]
4-tert-butylphenyldiphenylsulfonium
1,1,3,3,3-pentafluoro-2-(pivaloyloxy)propanesulfonate, [0292]
4-tert-butylphenyldiphenylsulfonium
2-(cyclohexanecarbonyl-oxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0293] 4-tert-butylphenyldiphenylsulfonium
2-(2-naphthoyloxy)-1,1,3,3,3-pentafluoropropanesulfonate, [0294]
4-tert-butylphenyldiphenylsulfonium
2-(1-adamantanecarbonyl-oxy)-1,1,3,3,3-pentafluoropropanesulfonate,
[0295] 4-tert-butylphenyldiphenylsulfonium
2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate, [0296]
4-tert-butylphenyldiphenylsulfonium
adamantanemethoxy-carbonyldifluoromethanesulfonate, [0297]
4-tert-butylphenyldiphenylsulfonium
1-(3-hydroxymethyl-adamantane)methoxycarbonyldifluoromethanesulfonate,
[0298] 4-tert-butylphenyldiphenylsulfonium
methoxycarbonyldifluoro-methanesulfonate, [0299]
2-oxo-2-phenylethylthiacyclopentanium
2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, [0300]
2-oxo-2-phenylethylthiacyclopentanium
2-cyclohexanecarbonyl-oxy-1,1,3,3,3-pentafluoropropanesulfonate,
[0301] triphenylsulfonium perfluoro(1,3-propylenebissulfonyl)imide,
[0302] triphenylsulfonium bis(pentafluoroethylsulfonyl)imide,
[0303]
2-(2,2,3,3,4,4,5,5-octafluoro-1-(nonafluorobutylsulfonyloxy-imino)pentyl)-
fluorene, [0304]
2-(2,2,3,3,4,4-pentafluoro-1-(nonafluorobutylsulfonyloxy-imino)butyl)fluo-
rene, [0305]
2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutylsulfonyl-oxyimino)hex-
yl)fluorene, [0306]
2-(2,2,3,3,4,4,5,5-octafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pen-
tafluoropropanesulfonyloxyimino)pentyl)fluorene, [0307]
2-(2,2,3,3,4,4-pentafluoro-1-(2-(cyclohexanecarbonyloxy)-1,1,3,3,3-pentaf-
luoropropanesulfonyloxyimino)butyl)fluorene, [0308] and
2-(2,2,3,3,4,4,5,5,6,6-decafluoro-1-(nonafluorobutyl-sulfonyloxyimino)hex-
yl)fluorene.
[0309] In the chemically amplified resist composition, the
photoacid generator (B) may be added in any desired amount as long
as the objects of the invention are not compromised. An appropriate
amount of the photoacid generator (B) is 0.1 to 30 parts, and more
preferably 0.5 to 20 parts by weight per 100 parts by weight of the
base resin in the composition. Less than 0.1 phr of the photoacid
generator (B) may lead to poor sensitivity whereas more than 30 phr
may lead to lower transparency and lower resolution and give rise
to a problem of foreign matter upon development and resist film
peeling. The photoacid generators may be used alone or in admixture
of two or more. The transmittance of the resist film can be
controlled by using an photoacid generator having a low
transmittance at the exposure wavelength and adjusting the amount
of the photoacid generator added.
[0310] It is noted that an acid diffusion controlling function may
be provided when two or more photoacid generators are used in
admixture provided that one photoacid generator is an onium salt
capable of generating a weak acid. Specifically, in a system using
a mixture of a photoacid generator capable of generating a strong
acid (e.g., fluorinated sulfonic acid) and an onium salt capable of
generating a weak acid (e.g., non-fluorinated sulfonic acid or
carboxylic acid), if the strong acid generated from the photoacid
generator upon exposure to high-energy radiation collides with the
unreacted onium salt having a weak acid anion, then a salt exchange
occurs whereby the weak acid is released and an onium salt having a
strong acid anion is formed. In this course, the strong acid is
exchanged into the weak acid having a low catalysis, incurring
apparent deactivation of the acid for enabling to control acid
diffusion.
[0311] If an onium salt capable of generating a strong acid and an
onium salt capable of generating a weak acid are used in admixture,
an exchange from the strong acid to the weak acid as above can take
place, but it never happens that the weak acid collides with the
unreacted onium salt capable of generating a strong acid to induce
a salt exchange. This is because of a likelihood of an onium cation
forming an ion pair with a stronger acid anion.
[0312] In the resist composition of the invention, there may be
added a compound which is decomposed with an acid to generate
another acid, that is, acid amplifier compound. For these
compounds, reference should be made to J. Photopolym. Sci. and
Tech., 8, 43-44, 45-46 (1995), and ibid., 9, 29-30 (1996).
[0313] Examples of the acid amplifier compound include
tert-butyl-2-methyl-2-tosyloxymethyl acetoacetate and
2-phenyl-2-(2-tosyloxyethyl)-1,3-dioxolane, but are not limited
thereto. Of well-known photoacid generators, many of those
compounds having poor stability, especially poor thermal stability
exhibit an acid amplifier-like behavior.
[0314] In the resist composition of the invention, an appropriate
amount of the acid amplifier compound is up to 10 parts, and
especially up to 5 parts by weight per 100 parts by weight of the
base resin. Excessive amounts of the acid amplifier compound make
diffusion control difficult, leading to degradation of resolution
and pattern profile.
[0315] Organic Solvent
[0316] The organic solvent (C) used herein may be any organic
solvent in which the base resin, acid generator, and other
components are soluble. Illustrative, non-limiting, examples of the
organic solvent include ketones such as cyclopentanone,
cyclohexanone, 4-methyl-2-pentanone and methyl amyl ketone;
alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol,
1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol
monomethyl ether, ethylene glycol monomethyl ether, propylene
glycol monoethyl ether, and ethylene glycol monoethyl ether; ethers
such as propylene glycol dimethyl ether and diethylene glycol
dimethyl ether; esters such as propylene glycol monomethyl ether
acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl
lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate,
ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl
propionate, and propylene glycol mono-tert-butyl ether acetate;
lactones such as .gamma.-butyrolactone; and carbonates such as
ethylene carbonate and propylene carbonate. These solvents may be
used alone or in combinations of two or more thereof. Of the above
organic solvents, it is recommended to use propylene glycol
monomethyl ether, PGMEA, cyclohexanone, .gamma.-butyrolactone,
ethyl lactate, and mixtures thereof because the base resin and acid
generator are most soluble therein.
[0317] Although the amount of the organic solvent used may be
determined as appropriate depending on the desired film thickness
or other factors, the preferred amount is 200 to 6,000 parts,
especially 400 to 4,000 parts by weight per 100 parts by weight of
the base resin.
[0318] Quencher
[0319] A quencher (D) may be optionally used in the resist
composition of the invention. The term "quencher" as used herein
has a meaning generally known in the art and refers to a compound
capable of suppressing the rate of diffusion when the acid
generated by the acid generator diffuses within the resist film.
The inclusion of quencher facilitates adjustment of resist
sensitivity and holds down the rate of acid diffusion within the
resist film, resulting in better resolution. In addition, it
suppresses changes in sensitivity following exposure and reduces
substrate and environment dependence, as well as improving the
exposure latitude and the pattern profile.
[0320] Examples of suitable quenchers include primary, secondary,
and tertiary aliphatic amines, mixed amines, aromatic amines,
heterocyclic amines, nitrogen-containing compounds with carboxyl
group, nitrogen-containing compounds with sulfonyl group,
nitrogen-containing compounds with hydroxyl group,
nitrogen-containing compounds with hydroxyphenyl group, alcoholic
nitrogen-containing compounds, amide derivatives, imide
derivatives, carbamate derivatives, and ammonium salts.
[0321] Also included are amine compounds of the following general
formula (B)-1.
N(X).sub.n(Y).sub.3-n (B)-1
In the formula, n is equal to 1, 2 or 3. The side chain X is
independently selected from groups of the following general
formulas (X)-1 to (X)-3. The side chain Y is independently hydrogen
or a straight, branched or cyclic C.sub.1-C.sub.20 alkyl group in
which some or all hydrogen atoms may be substituted by fluorine
atoms and which may contain an ether or hydroxyl group. Two or
three X may bond together to form a ring.
##STR00029##
In the formulas, R.sup.300, R.sup.302 and R.sup.305 are
independently straight or branched C.sub.1-C.sub.4 alkylene groups;
R.sup.301 and R.sup.304 are independently hydrogen or straight,
branched or cyclic C.sub.1-C.sub.50 alkyl groups in which some or
all hydrogen atoms may be substituted by fluorine atoms and which
may contain one or more hydroxyl, ether, ester groups or lactone
rings; R.sup.303 is a single bond or a straight or branched
C.sub.1-C.sub.4 alkylene group; R.sup.306 is a straight, branched
or cyclic C.sub.1-.sub.50 alkyl group in which some or all hydrogen
atoms may be substituted by fluorine atoms and which may contain
one or more hydroxyl, ether, ester groups or lactone rings.
[0322] Also useful are cyclic structure-bearing amine compounds
having the following general formula (B)-2.
##STR00030##
Herein X is as defined above, and R.sup.307 is a straight or
branched C.sub.2-C.sub.20 alkylene group in which some or all
hydrogen atoms may be substituted by fluorine atoms and which may
contain one or more carbonyl, ether, ester or sulfide groups.
[0323] Also included are cyano-bearing amine compounds having the
following general formulae (B)-3 to (B)-6.
##STR00031##
Herein X, R.sup.307 and n are as defined in formula (B)-1, and
R.sup.308 and R.sup.309 are each independently a straight or
branched C.sub.1-C.sub.4 alkylene group.
[0324] Also included are amine compounds of imidazole structure
having a polar functional group, represented by the general formula
(B)-7.
##STR00032##
Herein R.sup.310 is a straight, branched or cyclic C.sub.2-C.sub.50
alkyl group in which some or all hydrogen atoms may be substituted
by fluorine atoms and which has one or more polar functional
groups. The polar functional group is selected from among ester,
acetal, cyano, hydroxyl, carbonyl, ether, sulfide, and carbonate
groups and mixtures thereof. R.sup.311, R.sup.312 and R.sup.313 are
each independently a hydrogen atom, a straight, branched or cyclic
C.sub.1-C.sub.10 alkyl group, aryl group or aralkyl group.
[0325] Further included are amine compounds of benzimidazole
structure having a polar functional group, represented by the
general formula (B)-8.
##STR00033##
Herein R.sup.314 is hydrogen, a straight, branched or cyclic
C.sub.1-C.sub.50 alkyl group, aryl group or aralkyl group.
R.sup.315 is a straight, branched or cyclic C.sub.1-C.sub.50 alkyl
group in which some or all hydrogen atoms may be substituted by
fluorine atoms and which may have one or more polar functional
groups selected from ester, acetal, cyano, hydroxyl, carbonyl,
ether, sulfide, and carbonate groups and mixtures thereof.
[0326] Further included are heterocyclic nitrogen-containing
compounds having a polar functional group, represented by the
general formulae (B)-9 and (B)-10.
##STR00034##
Herein A is a nitrogen atom or .ident.C--R.sup.322. B is a nitrogen
atom or .ident.C--R.sup.323. R.sup.316 is a straight, branched or
cyclic C.sub.2-C.sub.50 alkyl group in which some or all hydrogen
atoms may be substituted by fluorine atoms and which has one or
more polar functional groups, the polar functional group being
selected from among ester, acetal, cyano, hydroxyl, carbonyl,
ether, sulfide, and carbonate groups and mixtures thereof.
R.sup.317, R.sup.318, R.sup.319 and R.sup.320 are each
independently hydrogen, a straight, branched or cyclic
C.sub.1-C.sub.10, alkyl group or aryl group, or a pair of R.sup.317
and R.sup.318 and a pair of R.sup.319 and R.sup.320, taken
together, may form a benzene, naphthalene or pyridine ring with the
carbon atoms to which they are attached. R.sup.321 is hydrogen, a
straight, branched or cyclic C.sub.1-C.sub.10 alkyl group or aryl
group. R32.sup.2 and R.sup.323 each are hydrogen, a straight,
branched or cyclic C.sub.1-C.sub.10 alkyl group or aryl group, or a
pair of R.sup.321 and R.sup.323, taken together, may form a benzene
or naphthalene ring with the carbon atoms to which they are
attached.
[0327] Also included are organic nitrogen-containing compounds
having an aromatic carboxylic acid ester structure, represented by
the general formulae (B)-11 to (B)-14.
##STR00035##
Herein R.sup.324 is a C.sub.6-C.sub.20 aryl group or
C.sub.4-C.sub.20 hetero-aromatic group, in which some or all
hydrogen atoms may be replaced by halogen atoms, straight, branched
or cyclic C.sub.1-C.sub.20 alkyl groups, C.sub.6-C.sub.20 aryl
groups, C.sub.7-C.sub.20 aralkyl groups, C.sub.1-C.sub.10 alkoxy
groups, C.sub.1-C.sub.10 acyloxy groups or C.sub.1-C.sub.10
alkylthio groups. R.sup.325 is CO.sub.2R.sup.326, OR.sup.327 or
cyano group. R.sup.326 is a C.sub.1-C.sub.10 alkyl group, in which
some methylene groups may be replaced by oxygen atoms. R.sup.327 is
a C.sub.1-C.sub.10 alkyl or acyl group, in which some methylene
groups may be replaced by oxygen atoms. R.sup.328 is a single bond,
methylene, ethylene, sulfur atom or --O(CH.sub.2CH.sub.2O).sub.n--
group wherein n is 0, 1, 2, 3 or 4. R.sup.329 is hydrogen, methyl,
ethyl or phenyl. X is a nitrogen atom or CR.sup.330. Y is a
nitrogen atom or CR.sup.331. Z is a nitrogen atom or CR.sup.332.
R.sup.330, R.sup.331 and R.sup.332 are each independently hydrogen,
methyl or phenyl. Alternatively, a pair of R.sup.330 and R.sup.331
or a pair of R.sup.331 and R.sup.332 may bond together to form a
C.sub.6-C.sub.20 aromatic ring or C.sub.2-C.sub.20 hetero-aromatic
ring with the carbon atoms to which they are attached.
[0328] Further included are amine compounds of
7-oxanorbornane-2-carboxylic ester structure, represented by the
general formula (B)-15.
##STR00036##
Herein R.sup.333 is hydrogen or a straight, branched or cyclic
C.sub.1-C.sub.10 alkyl group. R.sup.334 and R.sup.335 are each
independently a C.sub.1-C.sub.20 alkyl group, C.sub.6-C.sub.20 aryl
group or C.sub.7-C.sub.20 aralkyl group, which may contain one or
more polar functional groups selected from among ether, carbonyl,
ester, alcohol, sulfide, nitrile, amine, imine, and amide and in
which some hydrogen atoms may be replaced by halogen atoms.
R.sup.334 and R.sup.335, taken together, may form a heterocyclic or
hetero-aromatic ring of 2 to 20 carbon atoms with the nitrogen atom
to which they are attached.
[0329] Illustrative examples of the quencher used herein are given
below, but not limited thereto.
[0330] Examples of suitable primary aliphatic amines include
methylamine, ethylamine, n-propylamine, isopropylamine,
n-butylamine, isobutylamine, sec-butylamine, tert-butylamine,
pentylamine, tert-amylamine, cyclopentylamine, hexylamine,
cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine,
dodecylamine, cetylamine, methylenediamine, ethylenediamine, and
tetraethylenepentamine. Examples of suitable secondary aliphatic
amines include dimethylamine, diethylamine, di-n-propylamine,
diisopropylamine, di-n-butylamine, diisobutylamine,
di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine,
dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine,
didecylamine, didodecylamine, dicetylamine,
N,N-dimethylmethylenediamine, N,N-dimethylethylenediamine, and
N,N-dimethyltetraethylenepentamine. Examples of suitable tertiary
aliphatic amines include trimethylamine, triethylamine,
tri-n-propylamine, triisopropylamine, tri-n-butylamine,
triisobutylamine, tri-sec-butylamine, tripentylamine,
tricyclopentylamine, trihexylamine, tricyclohexylamine,
triheptylamine, trioctylamine, trinonylamine, tridecylamine,
tridodecylamine, tricetylamine,
N,N,N',N'-tetramethylmethylenediamine,
N,N,N',N'-tetramethylethylenediamine, and
N,N,N',N'-tetramethyltetraethylenepentamine.
[0331] Examples of suitable mixed amines include
dimethylethylamine, methylethylpropylamine, benzylamine,
phenethylamine, and benzyldimethylamine. Examples of suitable
aromatic and heterocyclic amines include aniline derivatives (e.g.,
aniline, N-methylaniline, N-ethylaniline, N-propylaniline,
N,N-dimethylaniline, N,N-bis(hydroxyethyl)aniline, 2-methylaniline,
3-methylaniline, 4-methylaniline, ethylaniline, propylaniline,
dimethylaniline, 2,6-diisopropylaniline, trimethylaniline,
2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline,
2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine),
diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine,
phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole
derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole,
2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole),
oxazole derivatives (e.g., oxazole and isooxazole), thiazole
derivatives (e.g., thiazole and isothiazole), imidazole derivatives
(e.g., imidazole, 4-methylimidazole, and
4-methyl-2-phenylimidazole), pyrazole derivatives, furazane
derivatives, pyrroline derivatives (e.g., pyrroline and
2-methyl-1-pyrroline), pyrrolidine derivatives (e.g., pyrrolidine,
N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone),
imidazoline derivatives, imidazolidine derivatives, pyridine
derivatives (e.g., pyridine, methylpyridine, ethylpyridine,
propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine,
dimethylpyridine, trimethylpyridine, triethylpyridine,
phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine,
diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine,
dimethoxypyridine, 4-pyrrolidinopyridine,
2-(1-ethylpropyl)pyridine, aminopyridine, and
dimethylaminopyridine), pyridazine derivatives, pyrimidine
derivatives, pyrazine derivatives, pyrazoline derivatives,
pyrazolidine derivatives, piperidine derivatives, piperazine
derivatives, morpholine derivatives, indole derivatives, isoindole
derivatives, 1H-indazole derivatives, indoline derivatives,
quinoline derivatives (e.g., quinoline and
3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline
derivatives, quinazoline derivatives, quinoxaline derivatives,
phthalazine derivatives, purine derivatives, pteridine derivatives,
carbazole derivatives, phenanthridine derivatives, acridine
derivatives, phenazine derivatives, 1,10-phenanthroline
derivatives, adenine derivatives, adenosine derivatives, guanine
derivatives, guanosine derivatives, uracil derivatives, and uridine
derivatives.
[0332] Examples of suitable nitrogen-containing compounds with
carboxyl group include aminobenzoic acid, indolecarboxylic acid,
and amino acid derivatives (e.g. nicotinic acid, alanine, alginine,
aspartic acid, glutamic acid, glycine, histidine, isoleucine,
glycylleucine, leucine, methionine, phenylalanine, threonine,
lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine). A
typical nitrogen-containing compound with sulfonyl group is
3-pyridinesulfonic acid. Examples of suitable nitrogen-containing
compounds with hydroxyl group, nitrogen-containing compounds with
hydroxyphenyl group, and alcoholic nitrogen-containing compounds
include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol,
3-indolemethanol hydrate, monoethanolamine, diethanolamine,
triethanolamine, N-ethyldiethanolamine, N,N-diethylethanolamine,
triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol,
3-amino-1-propanol, 4-amino-1-butanol,
4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine,
1-(2-hydroxyethyl)piperazine,
1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidine ethanol,
1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone,
3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol,
8-hydroxyjulolidine, 3-quinuclidinol, 3-tropanol,
1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol,
N-(2-hydroxyethyl)phthalimide, and
N-(2-hydroxyethyl)isonicotinamide. Examples of suitable amide
derivatives include formamide, N-methylformamide,
N,N-dimethylformamide, acetamide, N-methylacetamide,
N,N-dimethylacetamide, propionamide, benzamide, and
1-cyclohexylpyrrolidone. Suitable imide derivatives include
phthalimide, succinimide, and maleimide. Suitable carbamate
derivatives include N-tert-butoxycarbonyl-N,N-dicyclohexylamine,
N-tert-butoxycarbonylbenzimidazole, and oxazolidinone.
[0333] Suitable ammonium salts include [0334] pyridinium
p-toluenesulfonate, [0335] triethylammonium p-toluenesulfonate,
[0336] trioctylammonium p-toluenesulfonate, [0337] triethylammonium
2,4,6-triisopropylbenzenesulfonate, [0338] trioctylammonium
2,4,6-triisopropylbenzenesulfonate, [0339] triethylammonium
camphorsulfonate, [0340] trioctylammonium camphorsulfonate, [0341]
tetramethylammonium hydroxide, tetraethylammonium hydroxide, [0342]
tetrabutylammonium hydroxide, [0343] benzyltrimethylammonium
hydroxide, [0344] tetramethylammonium p-toluenesulfonate, [0345]
tetrabutylammonium p-toluenesulfonate, [0346]
benzyltrimethylammonium p-toluenesulfonate, [0347]
tetramethylammonium camphorsulfonate, [0348] tetrabutylammonium
camphorsulfonate, [0349] benzyltrimethylammonium camphorsulfonate,
[0350] tetramethylammonium 2,4,6-triisopropylbenzenesulfonate,
[0351] tetrabutylammonium 2,4,6-triisopropylbenzenesulfonate,
[0352] benzyltrimethylammonium 2,4,6-triisopropylbenzenesulfonate,
[0353] tetramethylammonium acetate, tetrabutylammonium acetate,
[0354] benzyltrimethylammonium acetate, tetramethylammonium
benzoate, [0355] tetrabutylammonium benzoate, and [0356]
benzyltrimethylammonium benzoate.
[0357] Further examples of the tertiary amines include [0358]
tris(2-methoxymethoxyethyl)amine, [0359]
tris{2-(2-methoxyethoxy)ethyl}amine, [0360]
tris{2-(2-methoxyethoxymethoxy)ethyl}amine, [0361]
tris{2-(1-methoxyethoxy)ethyl}amine, [0362]
tris{2-(1-ethoxyethoxy)ethyl}amine, [0363]
tris{2-(1-ethoxypropoxy)ethyl}amine, [0364]
tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, [0365]
4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, [0366]
4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane, [0367]
1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, [0368]
1-aza-12-crown-4,1-aza-15-crown-5,1-aza-18-crown-6,
tris(2-formyloxyethyl)amine, tris(2-acetoxyethyl)amine, [0369]
tris(2-propionyloxyethyl)amine, tris(2-butyryloxyethyl)amine,
[0370] tris(2-isobutyryloxyethyl)amine,
tris(2-valeryloxyethyl)amine, [0371] tris(2-pivaloyloxyethyl)amine,
[0372] N,N-bis(2-acetoxyethyl)-2-(acetoxyacetoxy)ethylamine, [0373]
tris(2-methoxycarbonyloxyethyl)amine, [0374]
tris(2-tert-butoxycarbonyloxyethyl)amine, [0375]
tris[2-(2-oxopropoxy)ethyl]amine, [0376]
tris[2-(methoxycarbonylmethyl)oxyethyl]amine, [0377]
tris[2-(tert-butoxycarbonylmethyloxy)ethyl]amine, [0378]
tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine, [0379]
tris(2-methoxycarbonylethyl)amine, [0380]
tris(2-ethoxycarbonylethyl)amine, [0381]
tris(2-benzoyloxyethyl)amine, [0382]
tris[2-(4-methoxybenzoyloxy)ethyl]amine, [0383]
N,N-bis(2-hydroxyethyl)-2-(methoxycarbonyl)ethylamine, [0384]
N,N-bis(2-acetoxyethyl)-2-(methoxycarbonyl)ethylamine, [0385]
N,N-bis(2-hydroxyethyl)-2-(ethoxycarbonyl)ethylamine, [0386]
N,N-bis(2-acetoxyethyl)-2-(ethoxycarbonyl)ethylamine, [0387]
N,N-bis(2-hydroxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,
[0388]
N,N-bis(2-acetoxyethyl)-2-(2-methoxyethoxycarbonyl)ethylamine,
[0389]
N,N-bis(2-hydroxyethyl)-2-(2-hydroxyethoxycarbonyl)ethylamine,
[0390]
N,N-bis(2-acetoxyethyl)-2-(2-acetoxyethoxycarbonyl)ethylamine,
[0391]
N,N-bis(2-hydroxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]-ethylamine,
[0392]
N,N-bis(2-acetoxyethyl)-2-[(methoxycarbonyl)methoxycarbonyl]-ethyl-
amine, [0393]
N,N-bis(2-hydroxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, [0394]
N,N-bis(2-acetoxyethyl)-2-(2-oxopropoxycarbonyl)ethylamine, [0395]
N,N-bis(2-hydroxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylamine,
[0396]
N,N-bis(2-acetoxyethyl)-2-(tetrahydrofurfuryloxycarbonyl)-ethylami-
ne, [0397]
N,N-bis(2-hydroxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbo-
nyl]ethylamine, [0398]
N,N-bis(2-acetoxyethyl)-2-[(2-oxotetrahydrofuran-3-yl)oxy-carbonyl]ethyla-
mine, [0399]
N,N-bis(2-hydroxyethyl)-2-(4-hydroxybutoxycarbonyl)ethylamine,
[0400]
N,N-bis(2-formyloxyethyl)-2-(4-formyloxybutoxycarbonyl)-ethylamine,
[0401]
N,N-bis(2-formyloxyethyl)-2-(2-formyloxyethoxycarbonyl)-ethylamine-
, [0402] N,N-bis(2-methoxyethyl)-2-(methoxycarbonyl)ethylamine,
[0403] N-(2-hydroxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,
[0404] N-(2-acetoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine,
[0405] N-(2-hydroxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, [0406]
N-(2-acetoxyethyl)-bis[2-(ethoxycarbonyl)ethyl]amine, [0407]
N-(3-hydroxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, [0408]
N-(3-acetoxy-1-propyl)-bis[2-(methoxycarbonyl)ethyl]amine, [0409]
N-(2-methoxyethyl)-bis[2-(methoxycarbonyl)ethyl]amine, [0410]
N-butyl-bis[2-(methoxycarbonyl)ethyl]amine, [0411]
N-butyl-bis[2-(2-methoxyethoxycarbonyl)ethyl]amine, [0412]
N-methyl-bis(2-acetoxyethyl)amine, [0413]
N-ethyl-bis(2-acetoxyethyl)amine, [0414]
N-methyl-bis(2-pivaloyloxyethyl)amine, [0415]
N-ethyl-bis[2-(methoxycarbonyloxy)ethyl]amine, [0416]
N-ethyl-bis[2-(tert-butoxycarbonyloxy)ethyl]amine, [0417]
tris(methoxycarbonylmethyl)amine, [0418]
tris(ethoxycarbonylmethyl)amine, [0419]
N-butyl-bis(methoxycarbonylmethyl)amine, [0420]
N-hexyl-bis(methoxycarbonylmethyl)amine, and [0421]
.beta.-(diethylamino)-.delta.-valerolactone.
[0422] Illustrative examples of the amine compounds include [0423]
1-[2-(methoxymethoxy)ethyl]pyrrolidine, [0424]
1-[2-(methoxymethoxy)ethyl]piperidine, [0425]
4-[2-(methoxymethoxy)ethyl]morpholine, [0426]
1-[2-(methoxymethoxy)ethyl]imidazole, [0427]
1-[2-(methoxymethoxy)ethyl]benzimidazole, [0428]
1-[2-(methoxymethoxy)ethyl]-2-phenylbenzimidazole, [0429]
1-[2-[(2-methoxyethoxy)methoxy]ethyl]pyrrolidine, [0430]
1-[2-[(2-methoxyethoxy)methoxy]ethyl]piperidine, [0431]
4-[2-[(2-methoxyethoxy)methoxy]ethyl]morpholine, [0432]
1-[2-[(2-methoxyethoxy)methoxy]ethyl]imidazole, [0433]
1-[2-[(2-methoxyethoxy)methoxy]ethyl]benzimidazole, [0434]
1-[2-[(2-methoxyethoxy)methoxy]ethyl]-2-phenylbenzimidazole, [0435]
1-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]pyrrolidine, [0436]
1-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]piperidine, [0437]
4-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]morpholine, [0438]
1-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]imidazole, [0439]
1-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]benzimidazole, [0440]
1-[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-2-phenylbenzimidazole,
[0441] 1-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]pyrrolidine, [0442]
1-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]piperidine, [0443]
4-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]morpholine, [0444]
1-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]imidazole, [0445]
1-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]benzimidazole, [0446]
1-[2-[2-(2-butoxyethoxy)ethoxy]ethyl]-2-phenylbenzimidazole, [0447]
1-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]pyrrolidine, [0448]
1-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]piperidine, [0449]
4-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]morpholine, [0450]
1-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]imidazole, [0451]
1-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]benzimidazole,
[0452]
1-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl]-2-phenyl-benzimidazole,
[0453] 4-[2-{2-[2-(2-butoxyethoxy)ethoxy]ethoxy}ethyl]morpholine,
[0454] 2-(1-pyrrolidinyl)ethyl acetate, 2-piperidinoethyl acetate,
[0455] 2-morpholinoethyl acetate, 2-(1-imidazolyl)ethyl acetate,
[0456] 2-(1-benzimidazolyl)ethyl acetate, [0457]
2-(2-phenyl-1-benzimidazolyl)ethyl acetate, [0458] 2-methoxyethyl
morpholinoacetate, [0459] 2-(1-pyrrolidinyl)ethyl 2-methoxyacetate,
[0460] 2-piperidinoethyl 2-methoxyacetate, [0461] 2-morpholinoethyl
2-methoxyacetate, [0462] 2-(1-imidazolyl)ethyl 2-methoxyacetate,
[0463] 2-(1-benzimidazolyl)ethyl 2-methoxyacetate, [0464]
2-(2-phenyl-1-benzimidazolyl)ethyl 2-methoxyacetate, [0465]
2-(1-pyrrolidinyl)ethyl 2-(2-methoxyethoxy)acetate, [0466]
2-piperidinoethyl 2-(2-methoxyethoxy)acetate, [0467]
2-morpholinoethyl 2-(2-methoxyethoxy)acetate, [0468]
2-(1-imidazolyl)ethyl 2-(2-methoxyethoxy)acetate, [0469]
2-(1-benzimidazolyl)ethyl 2-(2-methoxyethoxy)acetate, [0470]
2-(2-phenyl-1-benzimidazolyl)ethyl 2-(2-methoxyethoxy)acetate,
[0471] 2-(1-pyrrolidinyl)ethyl
2-[2-(2-methoxyethoxy)ethoxy]acetate, [0472] 2-piperidinoethyl
2-[2-(2-methoxyethoxy)ethoxy]acetate, [0473] 2-morpholinoethyl
2-[2-(2-methoxyethoxy)ethoxy]acetate, [0474] 2-(1-imidazolyl)ethyl
2-[2-(2-methoxyethoxy)ethoxy]acetate, [0475]
2-(1-benzimidazolyl)ethyl 2-[2-(2-methoxyethoxy)ethoxy]acetate,
[0476] 2-(2-phenyl-1-benzimidazolyl)ethyl
2-[2-(2-methoxyethoxy)-ethoxy]acetate, [0477] 2-morpholinoethyl
butyrate, 2-morpholinoethyl hexanoate, [0478] 2-morpholinoethyl
octanoate, 2-morpholinoethyl decanoate, [0479] 2-morpholinoethyl
laurate, 2-morpholinoethyl myristate, [0480] 2-morpholinoethyl
palmitate, 2-morpholinoethyl stearate, [0481] 2-morpholinoethyl
behenate, 2-morpholinoethyl cholate, [0482] 2-morpholinoethyl
tris(O-acetyl)cholate, [0483] 2-morpholinoethyl
tris(O-formyl)cholate, [0484] 2-morpholinoethyl dehydrocholate,
[0485] 2-morpholinoethyl cyclopentanecarboxylate, [0486]
2-morpholinoethyl cyclohexanecarboxylate, [0487]
2-(1-pyrrolidinyl)ethyl 7-oxanorbornane-2-carboxylate, [0488]
2-piperidinoethyl 7-oxanorbornane-2-carboxylate, [0489]
2-morpholinoethyl 7-oxanorbornane-2-carboxylate, [0490]
2-(1-imidazolyl)ethyl 7-oxanorbornane-2-carboxylate, [0491]
2-(1-benzimidazolyl)ethyl 7-oxanorbornane-2-carboxylate, [0492]
2-(2-phenyl-1-benzimidazolyl)ethyl 7-oxanorbornane-2-carboxylate,
[0493] 2-morpholinoethyl adamantanecarboxylate, [0494]
2-(1-pyrrolidinyl)ethyl formate, 2-piperidinoethyl propionate,
[0495] 2-morpholinoethyl acetoxyacetate, [0496]
2-(1-pyrrolidinyl)ethyl methoxyacetate, [0497]
2-(1-pyrrolidinyl)ethyl benzoate, 2-piperidinoethyl benzoate,
[0498] 2-morpholinoethyl benzoate, 2-(1-imidazolyl)ethyl benzoate,
[0499] 2-(1-benzimidazolyl)ethyl benzoate, [0500]
2-(2-phenyl-1-benzimidazolyl)ethyl benzoate, [0501]
2-(1-pyrrolidinyl)ethyl 4-methoxybenzoate, [0502] 2-piperidinoethyl
4-methoxybenzoate, [0503] 2-morpholinoethyl 4-methoxybenzoate,
[0504] 2-(1-imidazolyl)ethyl 4-methoxybenzoate, [0505]
2-(1-benzimidazolyl)ethyl 4-methoxybenzoate, [0506]
2-(2-phenyl-1-benzimidazolyl)ethyl 4-methoxybenzoate, [0507]
2-(1-pyrrolidinyl)ethyl 4-phenylbenzoate, [0508] 2-piperidinoethyl
4-phenylbenzoate, [0509] 2-morpholinoethyl 4-phenylbenzoate, [0510]
2-(1-imidazolyl)ethyl 4-phenylbenzoate, [0511]
2-(1-benzimidazolyl)ethyl 4-phenylbenzoate, [0512]
2-(2-phenyl-1-benzimidazolyl)ethyl 4-phenylbenzoate, [0513]
2-(1-pyrrolidinyl)ethyl 1-naphthalenecarboxylate, [0514]
2-piperidinoethyl 1-naphthalenecarboxylate, [0515]
2-morpholinoethyl 1-naphthalenecarboxylate, [0516]
2-(1-imidazolyl)ethyl 1-naphthalenecarboxylate, [0517]
2-(1-benzimidazolyl)ethyl 1-naphthalenecarboxylate, [0518]
2-(2-phenyl-1-benzimidazolyl)ethyl 1-naphthalenecarboxylate, [0519]
2-(1-pyrrolidinyl)ethyl 2-naphthalenecarboxylate, [0520]
2-piperidinoethyl 2-naphthalenecarboxylate, [0521]
2-morpholinoethyl 2-naphthalenecarboxylate, [0522]
2-(1-imidazolyl)ethyl 2-naphthalenecarboxylate, [0523]
2-(1-benzimidazolyl)ethyl 2-naphthalenecarboxylate, [0524]
2-(2-phenyl-1-benzimidazolyl)ethyl 2-naphthalenecarboxylate, [0525]
4-[2-(methoxycarbonyloxy)ethyl]morpholine, [0526]
1-[2-(t-butoxycarbonyloxy)ethyl]piperidine, [0527]
4-[2-(2-methoxyethoxycarbonyloxy)ethyl]morpholine, [0528] methyl
3-(1-pyrrolidinyl)propionate, [0529] methyl 3-piperidinopropionate,
methyl 3-morpholinopropionate, [0530] methyl
3-(thiomorpholino)propionate, [0531] methyl
2-methyl-3-(1-pyrrolidinyl)propionate, [0532] ethyl
3-morpholinopropionate, [0533] methoxycarbonylmethyl
3-piperidinopropionate, [0534] 2-hydroxyethyl
3-(1-pyrrolidinyl)propionate, [0535] 2-acetoxyethyl
3-morpholinopropionate, [0536] 2-oxotetrahydrofuran-3-yl
3-(1-pyrrolidinyl)propionate, [0537] tetrahydrofurfuryl
3-morpholinopropionate, [0538] glycidyl 3-piperidinopropionate,
[0539] 2-methoxyethyl 3-morpholinopropionate, [0540]
2-(2-methoxyethoxy)ethyl 3-(1-pyrrolidinyl)propionate, [0541] butyl
3-morpholinopropionate, [0542] cyclohexyl 3-piperidinopropionate,
[0543] .alpha.-(1-pyrrolidinyl)methyl-.gamma.-butyrolactone, [0544]
.beta.-piperidino-.gamma.-butyrolactone,
.beta.-morpholino-.delta.-valerolactone, [0545] methyl
1-pyrrolidinylacetate, methyl piperidinoacetate, [0546] methyl
morpholinoacetate, methyl thiomorpholinoacetate, [0547] ethyl
1-pyrrolidinylacetate, etc.
[0548] Illustrative examples of the cyano-bearing amine compounds
include 3-(diethylamino)propiononitrile, [0549]
N,N-bis(2-hydroxyethyl)-3-aminopropiononitrile, [0550]
N,N-bis(2-acetoxyethyl)-3-aminopropiononitrile, [0551]
N,N-bis(2-formyloxyethyl)-3-aminopropiononitrile, [0552]
N,N-bis(2-methoxyethyl)-3-aminopropiononitrile, [0553]
N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropiononitrile, [0554]
methyl N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionate,
[0555] methyl
N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionate, [0556]
methyl N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropionate,
[0557] N-(2-cyanoethyl)-N-ethyl-3-aminopropiononitrile, [0558]
N-(2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropiononitrile, [0559]
N-(2-acetoxyethyl)-N-(2-cyanoethyl)-3-aminopropiononitrile, [0560]
N-(2-cyanoethyl)-N-(2-formyloxyethyl)-3-aminopropiononitrile,
[0561] N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropiononitrile,
[0562]
N-(2-cyanoethyl)-N-[2-(methoxymethoxy)ethyl]-3-aminopropiono-nitrile,
[0563]
N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl)-3-aminopropiononitrile,
[0564]
N-(3-acetoxy-1-propyl)-N-(2-cyanoethyl)-3-aminopropiononitrile,
[0565]
N-(2-cyanoethyl)-N-(3-formyloxy-1-propyl)-3-aminopropiono-nitrile,
[0566]
N-(2-cyanoethyl)-N-tetrahydrofurfuryl-3-aminopropiononitrile,
[0567] N,N-bis(2-cyanoethyl)-3-aminopropiononitrile, [0568]
diethylaminoacetonitrile, [0569]
N,N-bis(2-hydroxyethyl)aminoacetonitrile, [0570]
N,N-bis(2-acetoxyethyl)aminoacetonitrile, [0571]
N,N-bis(2-formyloxyethyl)aminoacetonitrile, [0572]
N,N-bis(2-methoxyethyl)aminoacetonitrile, [0573]
N,N-bis[2-(methoxymethoxy)ethyl]aminoacetonitrile, [0574] methyl
N-cyanomethyl-N-(2-methoxyethyl)-3-aminopropionate, [0575] methyl
N-cyanomethyl-N-(2-hydroxyethyl)-3-aminopropionate, [0576] methyl
N-(2-acetoxyethyl)-N-cyanomethyl-3-aminopropionate, [0577]
N-cyanomethyl-N-(2-hydroxyethyl)aminoacetonitrile, [0578]
N-(2-acetoxyethyl)-N-(cyanomethyl)aminoacetonitrile, [0579]
N-cyanomethyl-N-(2-formyloxyethyl)aminoacetonitrile, [0580]
N-cyanomethyl-N-(2-methoxyethyl)aminoacetonitrile, [0581]
N-cyanomethyl-N-[2-(methoxymethoxy)ethyl)aminoacetonitrile, [0582]
N-cyanomethyl-N-(3-hydroxy-1-propyl)aminoacetonitrile, [0583]
N-(3-acetoxy-1-propyl)-N-(cyanomethyl)aminoacetonitrile, [0584]
N-cyanomethyl-N-(3-formyloxy-1-propyl)aminoacetonitrile, [0585]
N,N-bis(cyanomethyl)aminoacetonitrile, [0586]
1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, [0587]
4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, [0588]
1-piperidineacetonitrile, 4-morpholineacetonitrile, [0589]
cyanomethyl 3-diethylaminopropionate, [0590] cyanomethyl
N,N-bis(2-hydroxyethyl)-3-aminopropionate, [0591] cyanomethyl
N,N-bis(2-acetoxyethyl)-3-aminopropionate, [0592] cyanomethyl
N,N-bis(2-formyloxyethyl)-3-aminopropionate, [0593] cyanomethyl
N,N-bis(2-methoxyethyl)-3-aminopropionate, [0594] cyanomethyl
N,N-bis[2-(methoxymethoxy)ethyl]-3-aminopropionate, [0595]
2-cyanoethyl 3-diethylaminopropionate, [0596] 2-cyanoethyl
N,N-bis(2-hydroxyethyl)-3-aminopropionate, [0597] 2-cyanoethyl
N,N-bis(2-acetoxyethyl)-3-aminopropionate, [0598] 2-cyanoethyl
N,N-bis(2-formyloxyethyl)-3-aminopropionate, [0599] 2-cyanoethyl
N,N-bis(2-methoxyethyl)-3-aminopropionate, [0600] 2-cyanoethyl
N,N-bis[2-(methoxymethoxy)ethyl]-3-amino-propionate, [0601]
cyanomethyl 1-pyrrolidinepropionate, [0602] cyanomethyl
1-piperidinepropionate, [0603] cyanomethyl 4-morpholinepropionate,
[0604] 2-cyanoethyl 1-pyrrolidinepropionate, [0605] 2-cyanoethyl
1-piperidinepropionate, and [0606] 2-cyanoethyl
4-morpholinepropionate.
[0607] The quenchers may be used alone or in admixture of two or
more. The quencher is preferably formulated in an amount of 0.001
to 5 parts, and especially 0.01 to 3 parts by weight, per 100 parts
by weight of the base resin. Less than 0.001 phr of the quencher
may achieve no addition effect whereas more than 5 phr may lead to
too low a sensitivity.
[0608] Surfactant
[0609] Optionally, the resist composition of the invention may
further comprise a surfactant which is commonly used for improving
the coating characteristics.
[0610] Illustrative, non-limiting, examples of the surfactant
include nonionic surfactants, for example, polyoxyethylene alkyl
ethers such as polyoxyethylene lauryl ether, polyoxyethylene
stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene
oleyl ether, polyoxyethylene alkylaryl ethers such as
polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol
ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan
fatty acid esters such as sorbitan monolaurate, sorbitan
monopalmitate, and sorbitan monostearate, and polyoxyethylene
sorbitan fatty acid esters such as polyoxyethylene sorbitan
monolaurate, polyoxyethylene sorbitan monopalmitate,
polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan
trioleate, and polyoxyethylene sorbitan tristearate; fluorochemical
surfactants such as EFTOP EF301, EF303 and EF352 (JEMCO Inc.),
Megaface F171, F172, F173, R08 and R30 (Dai-Nippon Ink &
Chemicals, Inc.), Fluorad FC-430, FC-431, FC-4430 and FC-4432
(Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-381, S-382,
SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10,
KH-20, KH-30 and KH-40 (Asahi Glass Co., Ltd.); organosiloxane
polymers KP341, X-70-092 and X-70-093 (Shin-Etsu Chemical Co.,
Ltd.), acrylic acid or methacrylic acid Polyflow No. 75 and No. 95
(Kyoeisha Ushi Kagaku Kogyo Co., Ltd.). Inter alia, FC-4430,
Surflon S-381, Surfynol E1004, KH-20 and KH-30 are preferred. They
may be used alone or in admixture.
[0611] In the chemically amplified resist composition, the
surfactant is preferably formulated in an amount of up to 2 parts,
and especially up to 1 part by weight, per 100 parts by weight of
the base resin.
[0612] In one embodiment wherein the immersion lithography is
applied to the resist composition of the invention, particularly in
the absence of a resist protective film, the resist composition may
have added thereto another surfactant having a propensity to
segregate at the resist surface after spin coating for achieving a
function of minimizing water penetration or leaching. The preferred
other surfactant is a polymeric surfactant which is insoluble in
water, but soluble in alkaline developer, and especially which is
water repellent and enhances water slippage.
[0613] Suitable polymeric surfactants are shown below, but not
limited thereto.
##STR00037##
Herein R.sup.01, R.sup.04, R.sup.07 and R.sup.014 are each
independently hydrogen or methyl, R.sup.02, R.sup.03, R.sup.015 and
R.sup.016 are each independently hydrogen, or straight, branched or
cyclic C.sub.1-C.sub.20 alkyl or fluoroalkyl, R.sup.02 and R.sup.03
or R.sup.015 and R.sup.016 may bond together to form a non-aromatic
ring with the carbon atom to which they are attached, and in the
ring-forming case, R.sup.02 and R.sup.03, or R.sup.015 and
R.sup.016 denote straight, branched or cyclic alkylene or
fluoroalkylene groups having 2 to 20 carbon atoms in total,
[0614] R.sup.0 is fluorine or hydrogen or may bond with R.sup.05 to
form a non-aromatic ring having 3 to 10 carbon atoms in total with
the carbon atom to which they are attached, R.sup.05 is straight,
branched or cyclic C.sub.1-C.sub.6 alkylene in which one or more
hydrogen atoms may be substituted by fluorine, R.sup.06 is straight
or branched C.sub.1-C.sub.10 alkyl in which one or more hydrogen
atoms are substituted by fluorine, R.sup.05 and R.sup.06 may bond
together to form a non-aromatic ring with the carbon atoms to which
they are attached, and in the ring-forming case, R.sup.05 and
R.sup.06 denote trivalent organic groups having 2 to 12 carbon
atoms in total,
[0615] R.sup.08 is a single bond or C.sub.1-C.sub.4 alkylene,
R.sup.010 and R.sup.011 are each independently hydrogen, fluorine,
methyl or trifluoromethyl, R.sup.012 and R.sup.013 are each
independently a single bond, --O-- or --CR.sup.018R.sup.019--,
R.sup.09, R.sup.018 and R.sup.019 are hydrogen, fluorine, methyl or
trifluoromethyl,
[0616] R.sup.017 is straight or branched C.sub.1-C.sub.4 alkylene,
or may bond with R.sup.015 and R.sup.016 to form a non-aromatic
ring with the carbon atom to which they are attached,
[0617] X.sup.1, X.sup.2 and X.sup.3 are each independently
--C(.dbd.O)--O--, --O-- or --C(.dbd.O)--R.sup.020--C(.dbd.O)--O--
wherein R.sup.020 is straight, branched or cyclic C.sub.1-C.sub.10
alkylene,
[0618] .alpha.-1, .alpha.-2, .alpha.-3 and .beta. are numbers in
the range: 0.ltoreq.(.alpha.-1)<1, 0.ltoreq.(.alpha.-2)<1,
0.ltoreq.(.alpha.-3)<1,
0<(.alpha.-1)+(.alpha.-2)+(.alpha.-3)<1, 0<.beta.<1,
and 0<(.alpha.-1)+(.alpha.-2)+(.alpha.-3)+.beta..ltoreq.1.
[0619] To the resist composition, the polymeric surfactant is added
in an amount of 0.001 to 20 parts, preferably 0.01 to 10 parts by
weight, per 100 parts by weight of the base polymer.
[0620] While the resist composition of the invention typically
comprises the hydrogenate ROMP polymer or base resin, acid
generator, organic solvent, quencher and surfactant as described
above, there may be added optional other ingredients such as
dissolution inhibitors, acidic compounds, stabilizers, and dyes.
Optional ingredients may be added in conventional amounts so long
as this does not compromise the objects of the invention.
[0621] Other Polymer
[0622] To the resist composition of the invention, another polymer
other than the inventive hydrogenated ROMP polymer may also be
added. The other polymers that can be added to the resist
composition are, for example, those polymers comprising units of
the following formula (R1) and/or (R2) and having a weight average
molecular weight of 1,000 to 500,000, especially 3,000 to 100,000
although the other polymers are not limited thereto.
##STR00038## ##STR00039##
[0623] Herein, R.sup.001 is hydrogen, methyl or
CH.sub.2CO.sub.2R.sup.003. R.sup.002 is hydrogen, methyl or
CO.sub.2R.sup.003. R.sup.003 is a straight, branched or cyclic
C.sub.1-C.sub.15 alkyl group. R.sup.004 is hydrogen or a monovalent
C.sub.1-C.sub.15 hydrocarbon group having a carboxyl or hydroxyl
group. At least one of R.sup.005 to R.sup.008 represents a
monovalent C.sub.1-C.sub.15 hydrocarbon group having a carboxyl or
hydroxyl group while the remaining R's independently represent
hydrogen or a straight, branched or cyclic C.sub.1-C.sub.15 alkyl
group. Alternatively, a combination of R.sup.005 to R.sup.008
(e.g., a pair of R.sup.005 and R.sup.006, or R.sup.006 and
R.sup.007) may bond together to form a ring with the carbon atom to
which they are attached, and in that event, at least one of
ring-forming R.sup.005 to R.sup.008 is a divalent C.sub.1-C.sub.15
hydrocarbon group having a carboxyl or hydroxyl group, while the
remaining R's are independently single bonds or straight, branched
or cyclic C.sub.1-C.sub.15 alkylene groups. R.sup.009 is a
monovalent C.sub.3-C.sub.15 hydrocarbon group containing a
--CO.sub.2-- partial structure. At least one of R.sup.010 to
R.sup.013 is a monovalent C.sub.1-C.sub.15 hydrocarbon group
containing a --CO.sub.2-- partial structure, while the remaining
R's are independently hydrogen or straight, branched or cyclic
C.sub.1-C.sub.15 alkyl groups. A combination of R.sup.010 to
R.sup.013 (e.g., R.sup.010 and R.sup.011, or R.sup.011 and
R.sup.012) may bond together to form a ring with the carbon atom to
which they are attached, and in that event, at least one of
ring-forming R.sup.010 to R.sup.013 is a divalent C.sub.1-C.sub.15
hydrocarbon group containing a --CO.sub.2-- partial structure,
while the remaining R's are independently single bonds or straight,
branched or cyclic C.sub.1-C.sub.15 alkylene groups. R.sup.014 is a
polycyclic C.sub.1-C.sub.15 hydrocarbon group or an alkyl group
containing a polycyclic hydrocarbon group. R.sup.015 is an acid
labile group. R.sup.016 is hydrogen or methyl. R.sup.017 is a
straight, branched or cyclic C.sub.1-C.sub.8 alkyl group. X is
CH.sub.2 or an oxygen atom. Letter k' is 0 or 1; a1', a2', a3',
b1', b2', b3', c1', c2', c3', d1', d2', d3', and e' are numbers
from 0 to less than 1, satisfying
a1'+a2'+a3'+b1'+b2'+b3'+c1'+c2'+c3'+d1'+d2'+d3'+e'=1; f', g', h',
i', and j' are numbers from 0 to less than 1, satisfying
f'+g'+h'+i'+j'=1.
[0624] The inventive polymer (hydrogenated ROMP polymer) and the
other polymer are preferably blended in a weight ratio from 100:0
to 10:90, more preferably from 100:0 to 20:80. If the blend ratio
of the inventive polymer is below this range, the resist
composition would become poor in some of the desired properties.
The properties of the resist composition can be adjusted by
properly changing the blend ratio of the inventive polymer.
[0625] The other polymer is not limited to one type and a mixture
of two or more other polymers may be added. The use of plural
polymers allows for easy adjustment of resist properties.
Process
[0626] Pattern formation using the resist composition of the
invention may be performed by well-known lithography processes. The
process generally involves coating, heat treatment (or prebaking),
exposure, heat treatment (post-exposure baking, PEB), and
development. If necessary, any additional steps may be added.
[0627] For pattern formation, the resist composition is first
applied onto a substrate (on which an integrated circuit is to be
formed, e.g., Si, SiO.sub.2, SiN, SiON, TiN, WSi, BPSG, SOG,
organic antireflective coating, Cr, CrO, CrON, MoSi, etc.) by a
suitable coating technique such as spin coating, roll coating, flow
coating, dip coating, spray coating or doctor coating. The coating
is prebaked on a hot plate at a temperature of 50 to 150.degree. C.
for 1 to 10 minutes, preferably 60 to 140.degree. C. for 1 to 5
minutes. The resulting resist film is generally 0.01 to 2.0 .mu.m
thick.
[0628] A relationship of a reduced thickness of resist film to an
etch selectivity ratio between resist film and processable
substrate imposes severer limits on the process. Under
consideration is the tri-layer process in which a resist layer, a
silicon-containing intermediate layer, an undercoat layer having a
high carbon density and high etch resistance, and a processable
substrate are laminated in sequence from top to bottom. On etching
with oxygen gas, hydrogen gas, ammonia gas or the like, a high etch
selectivity ratio is available between the silicon-containing
intermediate layer and the undercoat layer, which allows for
thickness reduction of the silicon-containing intermediate layer. A
relatively high etch selectivity ratio is also available between
the monolayer resist and the silicon-containing intermediate layer,
which allows for thickness reduction of the monolayer resist. The
method for forming the undercoat layer in this case includes a
coating and baking method and a CVD method. In the case of coating,
novolac resins and resins obtained by polymerization of fused
ring-containing olefins are used. In the CVD film formation,
reactant gases such as butane, ethane, propane, ethylene and
acetylene are used. For the silicon-containing intermediate layer,
either a coating method or a CVD method may be employed. The
coating method uses silsesquioxane, polyhedral oligomeric
silsesquioxane (POSS) and the like while the CVD method uses silane
gases as the reactant. The silicon-containing intermediate layer
may have an antireflection function with a light absorbing ability
and have photo-absorptive groups like phenyl groups, or it may be a
SiON film. An organic film may be formed between the
silicon-containing intermediate layer and the photoresist, and the
organic film in this case may be an organic antireflective coating.
After the photoresist film is formed, deionized water rinsing (or
post-soaking) may be carried out for extracting the photoacid
generator and the like from the film surface or washing away
particles, or a protective film may be coated.
[0629] With a mask having a desired pattern placed above the resist
film, the resist film is then exposed to radiation such as UV,
deep-UV, electron beam, x-ray, excimer laser light, .gamma.-ray and
synchrotron radiation. The exposure dose is preferably about 1 to
200 mJ/cm.sup.2, more preferably about 10 to 100 mJ/cm.sup.2. The
film is further baked on a hot plate at 60 to 150.degree. C. for 1
to 5 minutes, preferably at 80 to 120.degree. C. for 1 to 3 minutes
(post-exposure baking=PEB). Thereafter the resist film is developed
with a developer in the form of an aqueous base solution, for
example, 0.1 to 5 wt %, preferably 2 to 3 wt % aqueous solution of
tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes,
preferably 0.5 to 2 minutes by conventional techniques such as dip,
puddle and spray techniques. In this way, a desired resist pattern
is formed on the substrate. It is appreciated that the resist
composition of the invention is suited for nano-scale patterning
using such high-energy radiation as deep UV with a wavelength of
254 to 193 nm, vacuum UV with a wavelength of 157 nm, electron
beam, soft x-ray, x-ray, excimer laser light, .gamma.-ray and
synchrotron radiation, and best suited for nano-scale patterning
using high-energy radiation in the wavelength range of 180 to 200
nm.
[0630] Immersion lithography can be applied to the resist
composition of the invention. The ArF immersion lithography uses a
liquid having a refractive index of at least 1 and highly
transparent at the exposure wavelength such as deionized water or
alkanes as the immersion solvent. The immersion lithography
involves prebaking a resist film and exposing the resist film to
light through a projection lens, with deionized water or similar
liquid interposed between the resist film and the projection lens.
Since this allows projection lenses to be designed to a numerical
aperture (NA) of 1.0 or higher, formation of finer size patterns is
possible. The immersion lithography is important for the ArF
lithography to survive to the 45-nm node, with a further
development thereof being accelerated. In the case of immersion
lithography, deionized water rinsing (or post-soaking) may be
carried out after exposure for removing water droplets left on the
resist film, or a protective coating may be applied onto the resist
film after pre-baking, for preventing any leach-out from the resist
and improving water slip on the film surface. The resist protective
coating used in the immersion lithography is preferably formed from
a solution of a polymer having 1,1,1,3,3,3-hexafluoro-2-propanol
residue which is insoluble in water, but soluble in an alkaline
developer liquid, in a solvent selected from alcohols of at least 4
carbon atoms, ethers of 8 to 12 carbon atoms, and mixtures
thereof.
[0631] The water immersion lithography using a NA 1.35 lens
achieves an ultimate resolution of 40 to 38 nm at the maximum NA,
but cannot reach 32 nm. Efforts have been made to develop higher
refractive index materials in order to further increase NA. It is
the minimum refractive index among projection lens, liquid, and
resist film that determines the NA limit of lenses. In the case of
water immersion, the refractive index of water is the lowest in
comparison with the projection lens (refractive index 1.5 for
synthetic quartz) and the resist film (refractive index 1.7 for
prior art methacrylate-based film). Thus the NA of projection lens
is determined by the refractive index of water. Recent efforts
succeeded in developing a highly transparent liquid having a
refractive index of 1.65. In this situation, the refractive index
of projection lens made of synthetic quartz is the lowest,
suggesting a need to develop a projection lens material with a
higher refractive index. LuAG (lutetium aluminum garnet
Lu.sub.3Al.sub.5O.sub.12) having a refractive index of at least 2
is the most promising material. The resist composition of the
invention is applicable to immersion lithography using a high
refractive index liquid.
[0632] The process that now draws attention as the technology for
extending the life of the ArF lithography is a double patterning
process involving a first set of exposure and development to form a
first pattern and a second set of exposure and development to form
a second pattern between features of the first pattern. See Proc.
SPIE, Vol. 5754, p 1508 (2005). A number of double patterning
processes have been proposed. One exemplary process involves a
first set of exposure and development to form a photoresist pattern
having lines and spaces at intervals of 1:3, processing the
underlying layer of hard mask by dry etching, applying another
layer of hard mask thereon, a second set of exposure and
development of a photoresist film to form a line pattern in the
spaces of the first exposure, and processing the hard mask by dry
etching, thereby forming a line-and-space pattern at a half pitch
of the first pattern. An alternative process involves a first set
of exposure and development to form a photoresist pattern having
spaces and lines at intervals of 1:3, processing the underlying
layer of hard mask by dry etching, applying a photoresist layer
thereon, a second set of exposure and development to form a second
space pattern on the remaining hard mask portion, and processing
the hard mask by dry etching. In either process, the hard mask is
processed by two dry etchings.
[0633] While the former process requires two applications of hard
mask, the latter process uses only one layer of hard mask, but
requires to form a trench pattern which is difficult to resolve as
compared with the line pattern. The latter process includes the use
of a negative resist material in forming the trench pattern. This
allows for use of high contrast light as in the formation of lines
as a positive pattern. However, since the negative resist material
has a lower dissolution contrast than the positive resist material,
a comparison of the formation of lines from the positive resist
material with the formation of a trench pattern of the same size
from the negative resist material reveals that the resolution
achieved with the negative resist material is lower. After a wide
trench pattern is formed from the positive resist material by the
latter process, there may be applied a thermal flow method of
heating the substrate for shrinkage of the trench pattern, or a
RELACS method of coating a water-soluble film on the trench pattern
as developed and heating to induce crosslinking at the resist film
surface for achieving shrinkage of the trench pattern. These have
the drawbacks that the proximity bias is degraded and the process
is further complicated, leading to reduced throughputs.
[0634] Both the former and latter processes require two etchings
for substrate processing, leaving the issues of a reduced
throughput and deformation and misregistration of the pattern by
two etchings. One method that proceeds with a single etching is by
using a negative resist material in a first exposure and a positive
resist material in a second exposure. Another method is by using a
positive resist material in a first exposure and a negative resist
material in a higher alcohol of 4 or more carbon atoms, in which
the positive resist material is not dissolvable, in a second
exposure. However, these methods using negative resist materials
with low resolution entail degradation of resolution.
[0635] If first exposure is followed by second exposure at a
half-pitch shifted position, the optical energy of second exposure
offsets the optical energy of first exposure so that the contrast
becomes zero. If a contrast enhancement layer (CEL) is formed on
the resist film, the incident light to the resist film becomes
nonlinear so that the first and second exposures do not offset each
other. Thus an image having a half pitch is formed. See Jpn. J.
Appl. Phy. Vol. 33 (1994) p 6874-6877. It is expected that similar
effects are produced by using an acid generator capable of two
photon absorption to provide a nonlinear contrast.
[0636] The critical issue associated with double patterning is an
overlay accuracy between first and second patterns. Since the
magnitude of misregistration is reflected by a variation of line
size, an attempt to form 32-nm lines at an accuracy of 10%, for
example, requires an overlay accuracy within 3.2 nm. Since
currently available scanners have an overlay accuracy of the order
of 8 nm, a significant improvement in accuracy is necessary.
[0637] Now under investigation is the resist pattern freezing
technology involving forming a first resist pattern on a substrate,
taking any suitable means for insolubilizing the resist pattern
with respect to the resist solvent and alkaline developer, applying
a second resist thereon, and forming a second resist pattern in
space portions of the first resist pattern. With this freezing
technology, etching of the substrate is required only once, leading
to improved throughputs and avoiding the problem of misregistration
due to stress relaxation of the hard mask during etching. In the
freezing technology, development efforts are focused on the step of
forming a resist film on the first resist pattern and the optical
or thermal step of insolubilizing the resist pattern. The resist
composition of the invention is also applicable to such a process.
Examples of light used for the freezing purpose include preferably
light with a wavelength of up to 300 nm, more preferably up to 200
nm, specifically ArF excimer light of wavelength 193 nm, Xe.sub.2
excimer light of 172 nm, F.sub.2 excimer light of 157 nm, Kr.sub.2
excimer light of 146 nm, and Ar.sub.2 excimer light of 126 nm, and
the exposure dose in the case of light is preferably in the range
of 10 mJ/cm.sup.2 to 10 J/cm.sup.2. Irradiation from an excimer
laser of sub-200 nm wavelength, especially 193 nm, 172 nm, 157 nm,
146 nm, and 122 nm, or an excimer lamp not only causes the
photoacid generator to generate an acid, but also promotes
photo-induced crosslinking reaction. In a further example where a
thermal acid generator in the form of an ammonium salt is added to
a photoresist composition, specifically in an amount of 0.001 to 20
parts, more specifically 0.01 to 10 parts by weight per 100 parts
by weight of the base resin, an acid can be generated by heating.
In this case, acid generation and crosslinking reaction proceed
simultaneously. The preferred heating conditions include a
temperature of 100 to 300.degree. C., and especially 130 to
250.degree. C., and a time of 10 to 300 seconds. As a result, a
crosslinked resist film is formed which is insoluble in solvents
and alkaline developers. The resist composition of the invention
can be applied to the double patterning process discussed
above.
[0638] The hydrogenated ROMP polymer of the invention is improved
in light transmittance, dissolution in alkaline developer, and
etching resistance and useful as a base resin in photoresist
materials for the fabrication of microelectronic devices using UV
or DUV. The resist composition comprising the polymer as a base
resin lends itself to micropatterning with EB or DUV since it is
sensitive to high-energy radiation and has excellent sensitivity,
resolution, and etching resistance. Especially because of the
minimized absorption at the exposure wavelength of an ArF or KrF
excimer laser, a finely defined pattern having sidewalls
perpendicular to the substrate can easily be formed. According to
the method of the invention, any desired one of varying polymers
within the scope of formula [1] can be simply synthesized in high
yields by starting with a certain compound [2], and reacting it
with an optimum one selected from a variety of alkylating agents,
without a need for modifying the starting monomer. This enables to
easily tailor the performance of resist material so as to meet the
customer's demand. The invention is of great industrial worth.
EXAMPLE
[0639] Examples and Comparative Examples are given below by way of
illustration and not by way of limitation.
Example 1
Synthesis of Polymer P-1
[0640] A mixture of 10.0 g of a polymer (P-0, Mw=8,860,
Mw/Mn=1.93), 1.13 g of an alkylating agent (AA-1), 0.98 g of
triethylamine, and 40.0 g of N,N-dimethylformamide was heated and
stirred at 60.degree. C. for 24 hours. The reaction mixture was
cooled, and the excess of triethylamine was neutralized with
hydrochloric acid. This was followed by standard aqueous work-up
and concentration, obtaining a crude polymer. A solution of the
crude polymer in tetrahydrofuran was added to ultrapure water
whereupon the polymer precipitated. Subsequent filtration, water
washing and vacuum drying yielded 10.5 g of Polymer P-1 (yield
96%). On GPC analysis, the polymer had a weight average molecular
weight Mw of 9,040 and a dispersity Mw/Mn of 1.89. FIG. 1 shows a
.sup.1H-NMR spectrum (600 MHz, deuterated THF) of the polymer.
##STR00040##
Examples 2 to 8
Synthesis of Polymers P-2 to P-8
[0641] Polymers P-2 to P-8 were synthesized by the same procedure
as in Example 1 aside from using the starting polymer and
alkylating agent shown in Table 1.
TABLE-US-00001 TABLE 1 Yield, Starting Alkylating Example Polymer %
MW Mn polymer agent 2 P-2 94 9,240 1.90 SP-1 AA-2 3 P-3 97 9,240
1.90 SP-1 AA-3 4 P-4 94 9,130 1.89 SP-1 AA-4 5 P-5 99 9,000 1.89
SP-2 AA-1 6 P-6 97 9,140 1.99 SP-2 AA-3 7 P-7 92 9,550 2.03 SP-3
AA-5 8 P-8 95 8,090 2.06 SP-4 AA-6 (P-2) ##STR00041## ##STR00042##
##STR00043## ##STR00044## (P-3) ##STR00045## ##STR00046##
##STR00047## ##STR00048## (P-4) ##STR00049## ##STR00050##
##STR00051## ##STR00052## (P-5) ##STR00053## ##STR00054##
##STR00055## ##STR00056## (P-6) ##STR00057## ##STR00058##
##STR00059## ##STR00060## (P-7) ##STR00061## ##STR00062##
##STR00063## (P-8) ##STR00064## ##STR00065## ##STR00066##
##STR00067## ##STR00068## (SP-2) ##STR00069## ##STR00070##
##STR00071## (SP-3) ##STR00072## ##STR00073## (SP-4) ##STR00074##
##STR00075## ##STR00076## ##STR00077## (AA-2) ##STR00078## (AA-3)
##STR00079## (AA-4) ##STR00080## (AA-5) ##STR00081## (AA-6)
##STR00082##
[0642] Resist compositions were formulated using the inventive
polymers as the base resin and examined for resist properties.
Examples I-1 to I-8 and Comparative Examples II-1 to II-3
[0643] Resist compositions were prepared by using inventive
polymers (P-1 to P-8) or comparative polymers (CP-1 to CP-3, shown
below) as the base resin, and dissolving the polymer, an acid
generator and a basic compound in a solvent in accordance with the
formulation shown in Tables 2 and 3. These compositions were each
filtered through a Teflon.RTM. filter with a pore diameter of 0.2
.mu.m, thereby giving resist solutions.
##STR00083## ##STR00084##
[0644] These resist solutions were spin-coated onto silicon wafers
having an antireflective coating (ARC29A by Nissan Chemical
Industries, Ltd.) of 78 nm thick coated thereon, then baked at
100.degree. C. to 130.degree. C. for 60 seconds to give resist
films having a thickness of 250 nm. The resist films were exposed
using an ArF excimer laser stepper (Nikon Corporation, NA 0.68),
then baked (PEB) at 100.degree. C. to 130.degree. C. for 60
seconds, and puddle developed for 60 seconds with an aqueous
solution of 2.38% tetramethylammonium hydroxide (TMAH), thereby
forming 1:1 line-and-space patterns.
[0645] The wafer as developed was cut and the section observed
under a scanning electron microscope (SEM). The optimum exposure
(Eop, mJ/cm.sup.2) is defined as the exposure dose which provides a
1:1 resolution at the top and bottom of a 130 nm line-and-space
pattern. The resolution of a resist under test is defined as the
minimum line width (nm) of a line-and-space pattern that remains
separated at the optimum exposure, with smaller values indicating
better resolution. Also the dependency on exposure dose of line
width of a 130 nm line-and-space pattern was examined. Provided
that a line width of 130 nm .+-.10% (i.e., between 117 nm and 143
nm) was permissible, a ratio (%) of the exposure dose range
providing the permissible line width to the optimum exposure dose
is computed and reported as exposure latitude, with greater values
indicating better. Patterns having lines of gradually narrowing
width were formed by changing the exposure dose in increments, and
the minimum line width above which the lines of 130 nm
line-and-space pattern did not collapse was determined and reported
as collapse margin, with smaller values being better. Furthermore,
the lines of 130 nm line-and-space pattern were observed under SEM,
and an RMS value of line roughness was computed and reported as
line edge roughness (LER), with smaller values being better.
[0646] Table 2 shows the composition of resist materials in
Examples, and their test results of resolution at optimum
soft-baking (SB)/post-exposure baking (PEB) temperatures. Table 3
shows the composition and test results of resist materials in
Comparative Examples. In Tables 2 and 3, the acid generator,
quencher and solvent are as identified below. It is noted that the
solvent contained 0.01 wt % of surfactant (Asahi Glass Co.,
Ltd.).
[0647] TPSNf: triphenylsulfonium nonafluorobutanesulfonate
[0648] Q1: tris(methoxymethoxyethyl)amine
[0649] CyHO: cyclohexanone
TABLE-US-00002 TABLE 2 Acid Organic SB/PEB Exposure Collapse Resin
generator Quencher solvent temp. Eop Resolution latitude margin LER
Example (pbw) (pbw) (pbw) (pbw) (.degree. C.) (mJ/cm.sup.2) (nm)
(%) (nm) (nm) I-1 P-1 TPSNf Q1 CyHO 100/110 22.0 120 16 72 6.0 (80)
(1) (0.236) (640) I-2 P-2 TPSNf Q1 CyHO 100/110 23.0 120 16 78 5.9
(80) (1) (0.236) (640) I-3 P-3 TPSNf Q1 CyHO 100/110 24.0 110 18 96
5.5 (80) (1) (0.236) (640) I-4 P-4 TPSNf Q1 CyHO 110/110 28.0 120
22 99 6.2 (80) (1) (0.236) (640) I-5 P-5 TPSNf Q1 CyHO 100/110 25.0
120 20 70 5.9 (80) (1) (0.236) (640) I-6 P-6 TPSNf Q1 CyHO 100/110
25.0 110 20 99 6.0 (80) (1) (0.236) (640) I-7 P-7 TPSNf Q1 CyHO
100/100 19.0 120 18 98 4.8 (80) (1) (0.236) (640) I-8 P-8 TPSNf Q1
CyHO 110/120 26.0 110 25 78 4.5 (80) (1) (0.236) (640)
TABLE-US-00003 TABLE 3 Acid Organic SB/PEB Exposure Collapse
Comparative Resin generator Quencher solvent temp. Eop Resolution
latitude margin LER Example (pbw) (pbw) (pbw) (pbw) (.degree. C.)
(mJ/cm.sup.2) (nm) (%) (nm) (nm) II-1 CP-1 TPSNf TMMEA CyHO 100/110
26.0 120 10 102 6.5 (80) (1) (0.236) (640) II-2 CP-2 TPSNf TMMEA
CyHO 100/115 22.0 120 16 99 6.3 (80) (1) (0.236) (640) II-3 CP-3
TPSNf TMMEA CyHO 110/120 23.0 120 14 104 5.9 (80) (1) (0.236)
(640)
[0650] It is evident from Tables 2 and 3 that any desired resist
factor can be readily tailored by a choice of an optimum structure
among polymers varying within the scope of the invention. When
resist materials are subject to ArF excimer laser lithography,
various factors including resolution, exposure latitude, collapse
margin, and LER can be improved as desired.
[0651] Japanese Patent Application No. 2008-080605 is incorporated
herein by reference.
[0652] Although some preferred embodiments have been described,
many modifications and variations may be made thereto in light of
the above teachings. It is therefore to be understood that the
invention may be practiced otherwise than as specifically described
without departing from the scope of the appended claims.
* * * * *